Mowiol Brochure en KSE

Specialized in Specialities
KSE
Mowiol
Polyvinyl Alcohol
Mowiol History / Manufacture / Structure
A B C D E F G H
The Mowiol Range
Production of Mowiol Solutions
Properties of Mowiol Solutions
The Mowiol Film
Physiological Properties of Mowiol
Uses of Mowiol
Disposal of Mowiol
Contents A 1 2 2.1 2.2 3 3.1 3.2 Mowiol History / Manufacture / Structure Page History of Polyvinyl Alcohol Manufacture of Polyvinyl Alcohol Manufacture of Polyvinyl Acetate Hydrolysis (Saponification) Structure of Polyvinyl Alcohol Polymer Chain Interaction between Polyvinyl Alcohol Chains A1 A1 A1 A2 A2 A2 A3
B 1 1.0 1.1. 1.1.1 1.1.2 1.1.3 1.1.4 1.1.5 1.1.6 1.1.7 1.1.8 1.1.9 2 3 4 5
The Mowiol Range Page General Characteristics Application fields / Survey Analytical Chemistry of Mowiol Bulk density Volatile content Viscosity pH measurement Na 2O ash content Ester value Residual acetyl content Degree of hydrolysis Sieve analysis Water Absorption of Mowiol Granules Behaviour of Mowiol under the Effect of Temperature IR Spectroscopy Molar Mass and Degree of Polymerization of Mowiol B2 B3 B4 B4 B4 B4 B4 B4 B5 B5 B5 B6 B6+B7 B6 B8+B9 B 10
C 1 2 2.1 2.2 2.3 3 4
Production of Mowiol Solutions Page Solubility of Mowiol Determination of the relative Rate of Dissolution of Mowiol Partially hydrolysed Mowiol Grades Fully hydrolysed Mowiol Grades Rate of Dissolution of Mowiol Grades Industrial Production of Mowiol Solutions Other Solvents and Diluents for Mowiol C1 C1 C1+C2C6 C 1 + C 7 C 10 C 1 + C 2 C 10 C 11 C 11
D 1 2 2. 1 2. 2 3 3.1 3.2 4 4.1 4.1.1 5 6 6.1 6.1.1 6.1.2 6.2. 7 7.1 7.2 7.2.1 7.2.2 7.2.3 7.2.4 7.2.5 7.2.6 7.2.6.1 7.2.6.2 7.2.7 7.3
Properties of Mowiol Solutions Page Viscosity / Concentration / Temperature Concentration of Mowiol Solutions Refractive Index and Concentration Density and Concentration Stability of Mowiol Solutions in Storage Increase in Viscosity through Association Preservation Interfacial Properties of Mowiol Solutions Defoaming of Mowiol Solutions Special defoamers Electrical Conductivity of Mowiol Solutions Additives affecting Viscosity Additives which reduce Viscosity Reducing the viscosity by desolvation Reducing viscosity by chain-splitting Additives which increase Viscosity Compatibility of Mowiol Solutions with water-soluble and water-dilutable Substances Salt Solutions (Electrolytes) Water-soluble Polymers Oxidatively degraded potato starch Oxidatively degraded potato starch, modified Oxidatively degraded corn starch Clariant polyglycols (polyethylene glycol) Casein Melamine and urea formaldehyde resins Melamine resins Urea resins Solutions of different Mowiol grades Polymer Emulsions D 19 D 20 D 20 D 20 D 20 D 20 D 21 D 22 D 23 D 24 D 24 D 24 D 1 + D 2 D 11 D1 D 12 D 12 D 13 D 13 D 13 D 13 D 15 D 15 D 15 D 16 D 16 D 16 D 16 D 17 D 19
E 1 2 3 4
The Mowiol Film Page Water Absorption and Water Resistance of Mowiol Films Plasticizers Tear Strenght and Elongation at Break of cast Mowiol Films Gas Permeability E1 E3 E3 E5
E 5 5.1 5.2 6
The Mowiol Film Page Solvent Resistance of Mowiol Films Water-miscible Solvents Water-immiscible Solvents Electrophysical Properties of Mowiol Films E5 E5 E5 E5
F 1
Physiological Properties of Mowiol Page Toxicology / Assessment with Respect to Foodstuffs Legislation Other Information / Safety at Work F1 F1
G 1 1.1 1.1.1 1.1.2 1.1.3 1.2 1.2.1 1.2.2 1.3 1.3.1 1.3.2 1.4 1.4.1 1.4.2 1.4.3 1.4.4 1.5 1.5.1 1.5.2 1.5.3 1.6 1.6.1 1.6.2 1.6.3 1.7
Uses of Mowiol Page Uses based primarily on Physical Properties of Mowiol Mowiol as Emulsifier / Protective Colloid Mowiol in polymer emulsions Properties of polymer emulsions containing Mowiol Production of polymer emulsions by emulsion polymerization Mowiol as a Raw Material in the Textile Industry Raw material for sizing agents Raw material for finishing and as a temporary adhesive for screen printing Mowiol as Raw Material for Adhesives Water-activated adhesives and wet bonding Modification of emulsion adhesives Mowiol in the Paper Industry Coated papers Surface sizing Special papers Heat-sealable paper coatings Mowiol as Temporary Binder Ceramic compounds Ferrite cores Pelletizing Thermoplastic Processing of Mowiol Plasticizing Film extrusion Injection moulding Mowiol in Protective and Strippable Coatings G1 G1 G1 G2 G3 G3 G3 G5 G5 G5 G6 G6 G6 G6 G7 G7 G8 G8 G8 G9 G9 G9 G 10 G 12 G 12
G 1.8 1.9 1.10 1.11 1.12 1.12.1 1.12.2 1.13 1.13.1 1.13.2 1.13.3 1.13.4 1.13.5 1.14 1.15 1.16 1.17 1.18 1.19 2 2.1 2.2 2.3 2.4 2.4.1 2.4.2 2.5 2.6
Uses of Mowiol Page Solvent-resistant Dip-coated Mowiol Articles Mowiol as Release Agent for Casting and Laminating Resins Production of Detergents and Cleaning Agents with Mowiol Mowiol in Plant Protection Agents Mowiol in the Metal Industry Secondary brightener in electroplating Quenching baths for steel Mowiol in the Paint Industry Roller-applied filling compounds Wood primers Distempers and watercolours Emulsion paints Artist's pastes / finger paints Mowiol in the Building Industry Mowiol in Cosmetics Fluorescence Analysis Microencapsulation Replicas (Plant Physiology) Preservation and Restoration Applications based mainly on the Reactivity of Mowiol Acetalyzation / Polyvinyl Butyral / Mowital B Spinning and Hardening of Fibres Mowiol Sponges Consolidation of Nonwovens Glass fibre nonwovens Textile nonwovens Photosensitive Coatings Offset Printing Plate Coatings / Printing-Screen Lacquers / Colour Television Screens Printing Inks for Decor Papers G 23 G 12 G 12 G 14 G 15 G 15 G 15 G 16 G 16 G 16 G 17 G 17 G 17 G 18 G 18 G 18 G 18 G 19 G 19 G 19 G 19 G 19 G 20 G 20 + G 21 G 22 G 22 G 22 G 22
H 1 2
Disposal of Mowiol Page Wastewater / Biodegradation Recovery (Recycling) and final Disposal H1 H2
Foreword
Compared with the last edition of the Mowiol brochure which appeared in December 1991, this new version has been updated. The subjects dealt with have been corrected and revised to some extend as a result of a product range reduction.
In order to provide you with as full a picture as possible of the uses of polyvinyl alcohol, the edition also includes some fields of application of Mowiol which are perhaps less well-known. Numerous cross-references to other chapters or sections indicate inter-related parts of the text and are intended to further facilitate the understanding of individual statements.
The layout of the brochure has not changed. The coloured pages relate to the subject matter of the respective chapters.
We hope hat this new edition will again contribute towards extending the knowledge of the interesting and important product group polyvinyl alcohol, as well as assisting the understanding of the relationship between property range and uses of Mowiol.
R&D Department Kuraray Specialities Europe KSE June 2003
Mowiol History / Manufacture / Structure
Polyvinyl alcohols are manufactured by polymerization of vinyl acetate and subsequent alcoholysis of the polyvinyl acetate formed. Mowiol is produced in a modern plant in the Industriepark Hchst.
Mowiol - History / Manufacture / Structure Page
1 2 2.1 2.2 3 3.1 3.2
History of Polyvinyl Alcohol Manufacture of Polyvinyl Alcohol Manufacture of Polyvinyl Acetate Hydrolysis (Saponification) Structure of Polyvinyl Alcohol Polymer Chain Interaction between Polyvinyl Alcohol Chains
A1 A1 A1 A2 A2 A2 A3
Mowiol - History / Manufacture / Structure
A 1 History of Polyvinyl Alcohol

The discovery of polyvinyl alcohol (PVAL) dates back to the pioneering days of macromolecular chemistry. The companies involved at the beginning were Dr Alexander Wacker GmbH (Consortium fr Elektrochemische Industrie GmbH) and the Hoechst Works of IG Farbenindustrie AG, later Farbwerke Hoechst AG than Hoechst AG. Also prominent was Prof Hermann Staudinger, initially at the Swiss Federal Technical University (Zurich) and from 1926 onwards at the University of Freiburg im Breisgau. Today KSE continue the tradition in producing and distributing PVAL. The trade name of these products is Mowiol. Polyvinyl alcohol occupies a special place among the familiar synthetic polymers. The monomer, vinyl alcohol, is theoretically the enol form of acetaldehyde but cannot exist as a monomer in practice. Polyvinyl alcohol was discovered in 1915 by F Klatte. The stoichiometric saponification of polyvinyl acetate with caustic soda to yield polyvinyl alcohol was first described in 1924 by W O Herrmann and W Haehnel [1]. At around that time, work on polyvinyl esters and their derivates, begun as early as 1912 at Chemische Fabrik Griesheim Elektron by F Klatte and E Zacharias, was being resumed at the Hoechst Works of IG Farbenindutrie AG. An agreement between Wacker AG (Consortium) and the Hoechst Works of IG Farbenindustrie AG prevented a dispute over patents; so both companies were able to undertake industrialscale production of polyvinyl alcohol as early as the 1920s. The studies of polyvinyl alcohol by W O Herrmann and W Haehnel induced H Staudinger to carry out extensive work on this polymer, which is also of extraordinary scientific interest; and this made a major contribution to his basic findings on the structure of macromolecules and the mechanism of polymer-analogous reactions. Foreseeing the future importance of polyvinyl alcohol, H Staudinger worked closely with the Hoechst Works of IG Farbenindustrie AG even at the early stage. W Starck, a student of Staudinger's, who later became head of the plastic laboratory at Farbwerke Hoechst AG, dealt at lenghth in his thesis with the polymer-analogous transformation of polyvinyl acetate into polyvinyl alcohol. This work contributed greatly to the proof of H Staudinger's theory of the primary valency chain structure of macromolecules. It also mentioned for the first time the methanolysis of polyvinyl acetate to yield polyvinyl alcohol [2]. This transesterification principle is still used industrially by all polyvinyl alcohol manufacturers. The process was initially carried out discontinuously. In the early years, the principal application for polyvinyl alcohol was textile sizing. Contacts between Freiburg University and
Japanese scientists, including I Sakurada and T Tomanari, led to the industrial production of polyvinyl alcohol in Japan. Since its discovery, polyvinyl alcohol has found many uses and new ones are still being added. Continuous and more economical methods of manufacture have therefore become necessary.
Literature [1] Cons. fr Elektrochem. Ind. GmbH, DRP 450 286 (20.7.1924) [2] H Staudinger, K Frey, W Starck, Ber. Dtsch. Chem. Ges. 60, 1782 (1927)
A 2 Manufacture of Polyvinyl Alcohol

Polyvinyl alcohols are polymers of vinyl alcohol. As the latter cannot exist in free form, all polyvinyl alcohols have so far been manufactured by polymerization of vinyl acetate which, unlike vinyl alcohol, is stable. The polyvinyl acetate produced then undergoes alcoholysis. As the technical properties of polyvinyl alcohol depend in the first place on the molar mass and residual acetyl group content, industrial manufacturing processes are designed to ensure exact adherence to these parameters.
A 2.1
Manufacture of Polyvinyl Acetate
Polymerization takes place on the principle of radical chain polymerization in an organic solvent, usually methanol. The necessary radicals are provided by initiators with peroxy- or azogroups as a result of decomposition in the reaction mixture.
CH2 = CH n OCOCH3 Vinyl acetate
Inititiator
CH2 CH OCOCH3 n Polyvinyl acetate
The methanol in this performs several functions. During polymerization it acts as a chain transfer agent and, together with the type and quantity of initiator, enables the molar masses to be adjusted to various values. By evaporative cooling it also serves to remove the heat produced in polymerization, and finally it is used for alcoholysis of the polyvinyl acetate. For industrial application of the process it is important to note that high molar masses can be achieved only with relatively low methanol contents and low vinyl acetate conversion levels. This means that some of the vinyl acetate used has to be recovered in pure form and reused. At present both continuous and discontinuous processes are still in use for vinyl acetate polymerization. It is obvious that conti-
A1
nuous polymerization processes, as are used in the manufacture of Mowiol, yield end-products with more uniform properties.
A 2.2
Hydrolysis (Saponification)
A 3 Structure of Polyvinyl Alcohol

In order to understand the relationship between the structure and properties of polyvinyl alcohol, it is very important to know the structure of the polymer chain.
The polyvinyl acetate dissolved in methanol is converted to polyvinyl alcohol by hydrolysis (alcoholysis). The catalyst is sodium hydroxide.
CH2 CH OCOCH3 Polyvinyl acetate CH2 CH OH Polyvinyl alkohol n n
+n CH3OH Methanol
Catalyst
A 3.1
Polymer Chain
+n CH3OCOCH3 Methyl acetate
Assuming that the polymerization of vinyl acetate takes place mainly in head-tail-head-tail sequences, hydrolysis must be followed by a polyvinyl alcohol with a 1,3-glycol chain structure [1]. Accordingly, the polyvinyl alcohol has the following (idealized) structural formula:
By varying the catalyst concentration, reaction temperature and reaction time, it is possible to adjust the residual acetyl group content. In the chemistry and use of polyvinyl alcohols a distinction is therefore drawn between fully and partially hydrolysed and fully and partially saponified grades. Grades with a few standard residual acetyl group contents, however, are customary for most uses (page B 1). The nature of the distribution of the residual acetyl groups in the partially hydrolysed polyvinyl alcohol is determined by the choice of catalyst and, where solvents are used, by the nature of those solvents. Thus in alkaline alcoholysis the residual groups are distributed mainly in blocks [1] and in acid reactions they are mostly distributed statistically [2]. Like polymerization, alcoholysis of polyvinyl acetate at KSE is carried out continuously (belt-processing). This ensures that Mowiol is produced in uniform quality. One important stage after alcoholysis is the removal of the by-product sodium acetate. The method used by KSE for the purpose gives polyvinyl alcohols with low salt contents.
Literature [1] Y Sakaguchi, Z Sawada, M Koizumi, K Tamaki, Kobunshi Kagaku 23, 890 (1966) [2] K Noro, Br. Polym. J. 2, 128 (1970)
H C H H C OH
H C H H C OH
H C H H C OH
H C H H C OH
H C H
Many subsequent papers on the composition, structure and properties of pure polyvinyl alcohol have also noted deviations from the formula represented above; the most important of these are described below. 1,2-glycol structure Vinyl acetate not only polymerizes in the pattern given above; from time to time head-head-tail-tail sequences also occur and in the subsequent hydrolysis produce polyvinyl alcohol with a 1,2-glycol structure [26]. Structures of this kind affect the (degree of) swellability of polyvinyl alcohol (films) in water. Carbonyl groups It has been shown by chemical reactions and spectral analyses that terminal aldehyde groups may be present in the polyvinyl alcohol [7, 8]. In particular, where acetaldehyde is present during polymerization of the vinyl acetate, carbonyl groups occur in the chain in greater numbers [914]. Branching Slight branching of the PVAL chain occurs when the vinyl acetate is polymerized. The greater the reaction, the more branched is the polymer. Because of the relatively high reactivity of the polyvinyl acetate radicals, two kinds of branching are possible in principle:
A2
a) Acetyl chain branching:
CH2 CH OC=O CH2

These branched structures break down during hydrolysis and lead to a reduction in the average molar mass of the polyvinyl alcohol (hydrolysis breakdown) [15, 16]. b) Primary chain branching:
The situation is illustrated by considering the reaction products of syndiotactic or isotactic polyvinyl alcohol and aldehyde. As the diagram shows, in one case there is a cis-derivative of m-dioxane and in the other a trans-derivative [22]:
H OH OH RCHO
H O O
H R
Isotactic PVAL
Cis-4,6 derivative of m-dioxane
OH CH2 C O C=O CH3 or
H OH
RCHO H
H O O R
Syndiotactic PVAL
Trans-4,6 derivative of m-dioxane
CH CH O C=O CH3
Recent studies suggest that an increase in primary chain branching accompanies a decrease in polymerization [17]. Chain branching affects the rheology of aqueous polyvinyl alcohol solutions. Steric structure (Tacticity) Recent decades have seen major discoveries concerning the three-dimensional structure of the polyvinyl alcohol chain. The predominance of a syndiotactic or isotactic structure (as well as atactic components) is already established by the time the vinyl acetate is polymerized. Normally, syndiotactic chain growth takes precedence [1821], but in the radical reaction process a product with a predominantly atactic structure is produced (vide also front page of Chapter B).
Polyvinyl alcohols of different tacticity have different properties. During acetalyzation (see Section G 2.1) the isotactic sequences react first. The greatest resistance to water is shown by syndiotactic polyvinyl alcohols [23]. The overall properties of a polyvinyl alcohol are determined not only by the chain length but also by the juxtaposition of the syndiotactic and isotactic chain sequences, that of the 1,3- and 1,2glycol arrangements mentioned initially, and that of the residual acetyl and keto- or aldehyde groups. It is difficult however to assess analytically the effect of any individual parameter on the property profile of the polymer.
A 3.2
Interaction between Polyvinyl Alcohol Chains
There is a strongly marked tendency towards mutual orientation in polyvinyl alcohol chains because of their polarity, both in aqueous solution and in the solid state. I Sakurada has designed a structural model for such behaviour (page A4). The randomly interweaving polymer chains run parallel to one another in certain areas, indicating crystalline regions in the polymer. The tendency of polyvinyl alcohol chains to align themselves with one another increases with the regularity of the chain structure.
A3
The form of distribution influences important properties such as the melting point, the surface tension of aqueous solutions [36] and the emulsifying and protective colloid properties [37]. Fully hydrolysed polyvinyl alcohols In the range from about 97 to 100 mol% hydrolysis, the relationship between the degree of hydrolysis and properties of a polyvinyl alcohol produces very clear differences in the property profiles. In particular the crystallization tendency increases very sharply in this range and so, in consequence, does the crystallinity. The main result is a reduction in the cold-water solubility of the polyvinyl alcohol. I Sakurada's structural model of polyvinyl alcohol Of the various factors counteracting the orientation of the chains, the acetyl groups present in the molecule are the most powerful. Depending on the origin, type and thermal history of a polyvinyl alcohol, it is possible to determine the glass transition temperature [Tg] and crystallite melting point [Tk] by differential scanning calorimetry [DSC]. Tg ranges between 40 and 80 C, and Tk between 180 and 240C. The degree of crystallization in a polyvinyl alcohol has a major influence on the solubility and swellability of the polymer. In fully hydrolysed polyvinyl alcohols, heat treatment produces an increase in crystallization which, in turn, impairs their solubility in water [24]. This effect is less marked in polyvinyl alcohols containing acetyl groups. The crystallization tendency and crystallinity have been studied by many researchers, and some papers are cited here [2534]. Partially hydrolysed polyvinyl alcohols In theory, the partially hydrolysed grades may be considered as mixed polymers of vinyl alcohol and vinyl acetate, the vinyl alcohol content being so predominant that the whole molecule is water-soluble. In all but a few polyvinyl alcohol grades the acetyl content is generally some 11% by weight, corresponding to approx 88 mol% hydrolysis in the basic polyvinyl acetate and an ester value of some 140 mg KOH/g. The following aspects also need to be taken into account in considering the structure and properties of the partially hydrolysed polyvinyl alcohol grades: 1. Distribution of the residual acetyl groups in a polyvinyl alcohol chain (regular, irregular or in conglomerates/blocks) [35]. 2. The acetyl groups may be variously distributed among the chains of different lengths in any polyvinyl alcohol grade. The variety of factors affecting the property profile of any polyvinyl alcohol makes it essential for this raw material to be manufactured under reproducible conditions, eg in a continuous process, as indeed is used for Mowiol. A simplified representation (structural formula) of the partially and fully hydrolysed PVAL grades can be found in Chapter B on page B 6.
Literature [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] H Staudinger, K Frey und W Starck, Ber. Dtsch. Chem. Ges. 60, 1782 (1927) A Dunn, Chem. and Ind. 801 (1980) P J Flory und F S Leutner, J. Polym. Sci. 3, 380 (1948) P J Flory und F S Leutner, J. Polym. Sci. 3, 267 (1950) A D McLaren, R J Davis, J. Amer. Chem. Soc. 68, 1134 (1946) H E Harris, J G Pritchard, J. Polym. Sci. A 2, 3623 (1964) C S Marvel, G E Inskeep, J. Amer. Chem. Soc. 85, 1710 (1943) J Lloyd, J. Appl. Polym. Sci. 1, 70 (1959) M Matsumoto, K Imai, Y Kazusa, J. Polym. Sci. 28, 426 (1958) J T Clarke, R O Howard, W H Stockmeyer, Makromolek, Chem. 4446, 427 (1961) J T Clarke, E R Blout, J. Polym. Sci. 1, 419 (1946) G Takayama, J. Chem. Soc. Jap., Ind. Chem. Sect. 59, 1432 (1956) J Ukida, G Takayama, T Kominami, Chem. High Polymer (Japan) 11, 212 (1954) T Chitani, G Meshitsuka, A Matsumoto, Chem. High Polymer (Japan) 11, 337 (1954) K G Blaikie, R N Crozier, Ind. Eng. Chem. 28, 1155 (1936) O L Wheeler, E Lavin, R N Crozier, J. Polym. Sci. 9, 157 (1952) P Mehnert, Koll. Ztschr. u. Z. Polymere 251, 587 (1973) S Murahashi, S Nozakura, M Sumi, H Yuki, K Hatada, J. Polym. Sci. B 4, 65 (1966) J G Pritchard, R N Wollmer, W C Lawrence, W B Block, J. Polym. Sci. A 1, Vol. 4, 707 (1966) K Imai, M Matsumoto, Bull. Soc. Chem. (Japan) 36, 455 (1973) K Imai, M Matsumoto, J. Polym. Sci. 55, 335 (1961) M Matsumoto, Y Ohyanagi, J. Polym. Sci. 37, 558 (1959) J F Kenney, G W Willcockson, J. Polym. Sci. Polym. Chem. Ed. 4, 679698 (1966) I Sakurada, Y Nukushina, Y Sone, Kobunshi Kagaku 12, 506 (1955) F Halle, Kolloid Ztschr. 69, 324 (1934) F Halle und W Hofmann, Naturwissenschaften 45, 770 (1935) C W Brunn, Nature 161, 929 (1948) W J Priest, J. Polym. Sci. 6, 699 (1950) L Alexandru, M Oprish und A Chiocanel, Vysokomol Soedin 4, 613 (1962) S Imoto, Kogyo Kagaku Zasshi (Japan) 64, 1671 (1961) N Takahashi and K Onozato, Kogyo Kagaku Zasshi (Japan) 65, 2062 (1962) K Tsuboi and T Mochizuki, U. S. Pat. 3, 427, 298 (1969) K Tsuboi and T Mochizuki, Polymer Letters 1, 531 (1961) A Packter und M S Nerurkar, Polymer Letters 7, 761 (1969) R K Tubbs, J. Polym. Sci. A 3, 4181 (1965); 4, 623 (1966) S Hayashi, C Nakano, T Motoyama, Kobunshi Kagaku 21, 300 (1964) S Hayashi, C Nakano, T Motoyama, Kobunshi Kagaku 22, 354 (1965)
A4
The Mowiol Range
Polyvinyl alcohols differ in their characteristics and structure. This results in properties which can be utilized to advantage for the great many fields of application. The picture shows a vector model of commercial atactic polyvinyl alcohol produced by CAMD Computer Aided Molecular Design with transparent representation of the sterical sphere of influence of the atoms.
The Mowiol Range Page
1 1.0 1.1. 1.1.1 1.1.2 1.1.3 1.1.4 1.1.5 1.1.6 1.1.7 1.1.8 1.1.9 2 3 4 5
General Characteristics Application fields / Survey Analytical Chemistry of Mowiol Bulk density Volatile content Viscosity pH measurement Na 2O ash content Ester value Residual acetyl content Degree of hydrolysis Sieve analysis Water Absorption of Mowiol Granules Behaviour of Mowiol under the Effect of Temperature IR Spectroscopy Molar Mass and Degree of Polymerization of Mowiol
B2 B3 B4 B4 B4 B4 B4 B4 B5 B5 B5 B6 B6+B7 B6 B8+B9 B 10
The Mowiol Range
B 1 General Characteristics
Mowiol is the trade name of the polyvinyl alcohols marketed by KSE. These are manufactured from polyvinyl acetate by alcoholysis (see Section A 2.2) using a continuous process. By varying the degree of polymerization of the polyvinyl acetate and its degree of hydrolysis (saponification) the grades shown in Table 1 can be supplied. Taken together, the specific properties of a polyvinyl alcohol, eg 1,2-glycol content, tacticity, branching, average length and distribution of residual acetyl group sequences especially in partially hydrolysed grades , provide an individual property profile. Although not featured in the characteristic product data (see Section A 3.1), this profile can still be regarded as constant in products such as Mowiol which are manufactured by a continuous process. The Mowiol grades are supplied in the form of fine granules. If required, some grades are also available in a finer particle size, 200 m being the smallest size that can be supplied. Table 1 Technical data of the Mowiol range
Viscosity1) mPa s Partially hydrolysed Mowiol grades. Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Fully hydrolysed grades. Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol 15-79 3-83 4-88 5-88 8-88 18-88 23-88 26-88 40-88 47-88 30-92 3-96 3-98 4-98 6-98 10-98 20-98 56-98 28-99 15 3 4 5.5 8 18 23 26 40 47 30 3.3 3.5 4.5 6 10 20 56 28 2.0 0.5 0.5 0.5 1.0 1.5 1.5 1.5 2.0 2.0 2.0 0.5 0.5 0.5 1.0 1.0 1.5 4.0 2.0
In its original packaging, Mowiol can be stored in closed, dry rooms, at room temperature, for virtually unlimited periods. The applications of Mowiol derive from 1. its physical property profile, characterized in particular by its solubility in water, the specific colloidal characteristics of the aqueous solution (see Chapter D), its outstanding film formation and high binding power, 2. the chemical characteristics of these polymers, eg the reactivity of the numerous hydroxyl groups with other substances such as reactive resins, aldehydes, bichromates and other reactant compounds. In many applications of Mowiol the characteristics listed in 1. and 2. overlap and complement one another in an ideal fashion.
Degree of hydrolysis Ester value 2) (saponification) mg KOH/g mol % 81.5 82.6 87.7 87.7 87.7 87.7 87.7 87.7 87.7 87.7 92.4 97.2 98.4 98.4 98.4 98.4 98.4 98.4 99.4 2.2 2.2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.9 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 200 190 140 140 140 140 140 140 140 140 90 35 20 20 20 20 20 20 8
1) of
Residual acetyl content wt. % 15.4 14.6 10.8 10.8 10.8 10.8 10.8 10.8 10.8 10.8 6.9 2.7 1.5 1.5 1.5 1.5 1.5 1.5 0.6 1.6 1.5 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Max ash3) content % 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.0 1.0 0.5 0.5 0.5 0.5 1.0 0.5
20 20 10 10 10 10 10 10 10 10 10 5 5 5 5 5 5 5 5
Volatile matter (DIN 53 189): maximum 5 % (after 3 h drying at 105 C). pH of a 4 % solution in distilled water (DIN 19 260/61): 4.57 for partially and fully hydrolysed grades. Bulk density (DIN 53 468): approx 0.40.6 g cm3, depending on grade.4)
a 4% aqueous solution at 20 C (DIN 53 015) 2) (DIN 53 401) 3) calculated as Na O 2 4) approximate values only
Notes on nomenclature: The first figure in the grade number is the viscosity of the 4% aqueous solution at 20 C as a relative indication of the molar mass of the Mowiol. The second figure is the degree of hydrolysis
(saponification) of the polyvinyl acetate on which it is based (partially and fully hydrolysed Mowiol grades).
B2
The Mowiol Range
B 1.0 Application fields/Survey

Partially hydrolysed types
15-79 18-88 23-88 26-88 40-88 47-88 30-92 3-83 4-88 5-88 8-88 3-98
Fully hydrolysed types

10-98 20-98 56-98 28-99 4-98 6-98
Colour television screens Ceramic compounds Adhesives Cosmetics Photo sensitive coatings Mortar, Coatings, Tile adhesives Paper industry Pelletizing, Micro incapsulation Plant protective agent Polymerization Sponges Cleaning agent Protective and strippable coatings Textile sizing Release agent Textile Non wovens Water soluble films
Mowiol application fields (chapter G in detail)
Main application sectors
Possible application
B3
The Mowiol Range
B 1.1
Analytical Chemistry of Mowiol
The viscosity is determined immediately after dissolving and cooling to 20 0.1 C. The solutions must be free of air bubbles. B 1.1.4 pH measurement The pH is measured in a 4% aqueous solution using a pH electrode (for the standard commercial single rod measurement system see DIN 19 260, pH measurement, general terms, or DIN 19 261, pH measurement, terms for measuring methods). B 1.1.5 Na2 O ash content To determine the ash content, 4.5 5.0 g of a Mowiol sample is weighed into a nickel dish and burnt at approx. 700 C in a rapid asher. The residue is then treated for 1 h at 800 C in an oven. In a titration flask, 100 ml of hydrochloic acid = 0.015 mol/l is measured and then added to the hot nickel dish. After cooling, the nickel dish is removed and cleaned with de-ionized water. With a titroprocesser and a solution of sodium hydroxide the residue is titrated. In the same way, 100 ml of hydrochloric solution is titrated to determine a comparison value.
To determine the individual products of the Mowiol range it is necessary to have a knowledge of certain simple methods of chemical and physical investigation. B 1.1.1 Bulk density The bulk density of Mowiol granules measured in accordance with DIN 53 468 is approx 0.4 0.6 g cm 3 according to grade. B 1.1.2 Volatile content Mowiol is a technical product with a maximum volatile content of 5% (water and organic solvents). Method of determination (based on DIN 53 189): Approx 2 g of Mowiol are weighed into a calibrated glass dish with a diameter of approx 5 cm and dried approximately 3 hours to constant weight at 105 C. After cooling in an exsiccator the Mowiol is reweighed and the percentage weight difference calculated. B 1.1.3 Viscosity According to DIN 51 550 the viscosity is a measure of the internal friction occurring in the displacement of two adjacent liquid layers. Units: The unit of dynamic viscosity ( ) in the international system of units (SI) is 1 Pa s (Pascal second). The unit of kinematic viscosity ( ), (measured in an Ubbelohde viscometer), is cm 2 s1. The relationship between dynamic viscosity and kinematic viscosity is as follows: 1 cm2 s1 = 0,1 Pa s Solution density
Evaluation
WNa O-ash content = 2 WNa O-ash 2

content
(VB1 VSa) tNaOH CTitr.Ag. M1/2 Na2O MSa . 10
= mass of Na 2O-ash in % = consumption of NaOH-solution/ with blank sample = consumption of NaOH-solution/ with Mowiol sample = titer of the solution of NaOH = concentration of the solution of NaOH (0.1 mol/l) = half molar mass of Na 2O (31 g/mol) = weight of the sample in g = calculation factor (l in ml and %)
VB1 VSa tNaOH CTitr.Ag. M1/2 Na O 2 MSa 10
Method of determination: The viscosity of Mowiol solutions is measured on freshly made solutions using a Hppler falling-ball viscometer (DIN 53 015) or an Ubbelohde viscometer (capillary viscometer, DIN 51 562 and DIN 53 012). It is international practice to state the viscosity of 4% aqueous polyvinyl alcohol solutions at 20 C. The volatile content of the polyvinyl alcohol has to be taken into account during production of the solution (see Section B 1.1.2). For production of the Mowiol solution see Chapter C.
B4
The Mowiol Range
B 1.1.6 Ester value The term ester value (EV) connotes the number of mg KOH needed to neutralize the acid released from the ester by saponification in 1 g of substance. Method of determination (based on DIN 53 401): a. Partially hydrolysed grades: Approximately 1 g Mowiol is weighed into a 250-ml round-bottomed flask and mixed with 70 ml distilled water and 30 ml neutralized alcohol, then heated with reflux until it dissolves. After cooling it is neutralized against phenol phthalein with 0.1 n KOH (see Section B 1.1.6). When neutralization is complete, 50 ml 0.1 n KOH are added and the mixture is boiled for 1 hour with reflux. The excess caustic solution is back-titrated in the heat with 0.1 n HCI against phenol phthalein as indicator until the coloration fails to recur. A blank test is carried out at the same time. b. Fully hydrolysed grades: To avoid absorption of carbon dioxide from the air in the excess KOH, only 25 ml 0.1 n KOH are added to the Mowiol solution after neutralization and the solution is then heated for 30 min with reflux. The hot solution is mixed with 25 ml 0.1 n HCI and titrated against phenol phthalein with 0.1 n KOH after cooling. A blank test is carried out at the same time. Ester value (EV) = (a b) 5.61 E
Table 2 EV 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 H 100.0 99.9 99.8 99.8 99.7 99.6 99.5 99.4 99.4 99.3 99.2 99.1 99.0 99.0 98.9 98.8 98.7 98.6 98.6 98.5 98.4 98.3 98.2 98.2 98.1 98.0 97.9 97.8 97.8 97.7 97.6 97.5 97.4 97.3 97.3 97.2 97.1 97.0 96.9 96.8 96.8 96.7 96.6 96.5 96.4 96.3 96.3 96.2 96.1 96.0
Ester value (EV) in mg KOH/g and associated degree of hydrolysis (H) in mol % EV 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 69 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 H 95.9 95.8 95.8 95.7 95.6 95.5 95.4 95.3 95.2 95.2 95.1 95.0 94.9 94.8 94.7 94.6 94.5 94.5 94.4 94.3 94.2 94.1 94.0 93.9 93.8 93.8 93.7 93.6 93.5 93.4 93.3 93.2 93.1 93.1 93.0 92.9 92.8 92.7 92.6 92.5 92.4 92.3 92.2 92.2 92.1 92.0 91.9 91.8 91.7 91.6 EV 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 H 91.5 91.4 91.3 91.2 91.1 91.1 91.0 90.9 90.8 90.7 90.6 90.5 90.4 90.3 90.2 90.1 90.0 89.9 89.8 89.7 89.6 89.6 89.5 89.4 89.3 89.2 89.1 89.0 88.9 88.8 88.7 88.6 88.5 88.4 88.3 88.2 88.1 88.0 87.9 87.8 87.7 87.6 87.5 87.4 87.3 87.2 87.1 87.0 86.9 86.8 EV 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 H 86.7 86.6 86.5 86.4 86.3 86.2 86.1 86.0 85.9 85.8 85.7 85.6 85.5 85.4 85.3 85.2 85.1 85.0 84.9 84.8 84.7 84.6 84.5 84.4 84.3 84.2 84.1 84.0 83.9 83.8 83.7 83.6 83.5 83.4 83.2 83.1 83.0 82.9 82.8 82.7 82.6 82.5 82.4 82.3 82.2 82.1 82.0 71.9 81.7 81.6 EV 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 H 81.5 81.4 81.3 81.2 81.1 81.0 80.9 80.8 80.7 80.5 80.4 80.3 80.2 80.1 80.0 79.9 79.8 79.7 79.5 79.4 79.3 79.2 79.1 79.0 78.9 78.8 78.6 78.5 78.4 78.3 78.2 78.1 78.0 77.8 77.7 77.6 77.5 77.4 77.3 77.1 77.0 76.9 76.8 76.7 76.6 76.4 76.3 76.2 76.1 76.0 EV 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 H 75.8 75.7 75.6 75.7 75.4 75.3 75.1 75.0 74.9 74.8 74.6 74.5 74.4 74.3 74.2 74.0 73.9 73.8 73.7 73.6 73.4 73.3 73.2 73.1 72.9 72.8 72.7 72.6 72.4 72.3 72.2 72.1 71.9 71.8 71.7 71.6 71.4 71.3 71.2 71.0 70.9 70.8 70.7 70.5 70.4 70.3 70.1 70.0 69.9 69.7
a = consumption of ml 0.1 n KOH b = consumption of ml 0.1 n KOH in the blank test E = weighed quantity of Mowiol (dry) B 1.1.7 Residual acetyl content The residual acetyl content is calculated from the ester value as follows: EV 0.0767 = residual acetyl content (wt. %) B 1.1.8 Degree of hydrolysis The degree of hydrolysis (saponification) H indicates what percentage of the basic polyvinyl acetate molecule is saponified to polyvinyl alcohol. From the residual acetyl group content and thus the ester value EV, H is calculated by using the following formula: H in mol% = 100 0.1535 EV 100 0.0749 EV
100
A degree of hydrolysis of 100% means, therefore, hat the PVAL has no acetyl groups. Table 2 and Figure 1 illustrate this nonlinear relationship between the degree of hydrolysis and the ester value.
B5
The Mowiol Range
mg KOH/g 700 650 600 500 400
Ester value
B 2 Water Absorption of Mowiol Granules

If Mowiol granules are exposed to atmospheric air during storage, the gradually enter into equilibrium with the air humidity, Mowiol is not hygroscopic, however; so even at high relative humidity the Mowiol particles remain free-flowing and there is no danger of caking unless high pressure and temperature occur at the same time. Assuming that a thin layer of Mowiol granules enters into equilibrium with the ambient humidity within a week, Figures 2 and 3 show approximate values from gravimetric measurements of the conditioned storage of Mowiol grades at a constant temperature of 23 C and rising relative humidity of 15 93%. The curves for the partially hydrolysed Mowiol grades (Figure 2) rise sharply above a relative humidity of approximately 60%, whereas in fully hydrolysed Mowiol grades (Figure 3) the water content increases almost linearly with the relative humidity. All measurements relate to a single production batch.
300
200
140 100
20 0 10 30 50 70 90 100 mol% Degree of hydrolysis
B 3 Behavior of Mowiol under the Effect of Temperature

Where dry polyvinyl alcohol is heated for a long period, gaseous products may be given off at temperatures above 110C, depending on the duration and intensity of the heating. Thermogravimetric analysis shows distinct decomposition of the polymer in air at temperatures above 180 C.
Figure 1 Relationship between degree of hydolysis (mol %) and ester value (mg KOH/g)
B 1.1.9 Sieve analysis (to DIN 66 165) To determine its particle size distribution, Mowiol is screened with a sieving machine on test sieves to DIN 4188. The residues left on the test sieves and the amount passing through the finest test sieve are determined by weighing.
Literature [1] B Kaesche-Krischer, H J Heinrich, Chem. Ing. Techn. 32, 598, 740 (1960) [2] A S Dunn, R L Coley, B Duncalf, Soc. Chem. Ind., London 1968 ( Monograph)
B6
The Mowiol Range
% Water content
10
1 2 3 4 5
Mowiol 4-88 Mowiol 8-88 Mowiol 18-88 Mowiol 26-88 Mowiol 40-88
2 1 3 4 5
0 0
1 32 5 4
20
40
60
80 100 Relative humidity at 23 C
Figure 2 Water absorption of partially hydrolysed Mowiol grades in granular form
% Water content
10
1 2 3 4 5
Mowiol Mowiol Mowiol Mowiol Mowiol
4-98 10-98 20-98 56-98 28-99
4 1 5 2,3
4 1,3 2 5
0 0 20 40 60 80 100 Relative humidity at 23C
Figure 3 Water absorption of fully hydrolysed Mowiol grades in granular form
B7
The Mowiol Range
B 4 IR Spectroscopy
The infrared spectrum of a substance can be used for the qualitative determination of a chemical compound. Even in a mixture the presence or absence of certain components can be confirmed by this method. In particular, organic atom groupings such as CH, C = O, C N, COC and COH produce characteristic resonance oscillations in the range between 4000 cm1 and 800 cm1, and experience shows that these can be classified. The Mowiol samples can basically be prepared in two ways: Either the aqueous solution is dried to an ultrafine film after filtering or centrifuging, or potassium bromide is moistened with a drop of Mowiol solution, dried and pressed to form a pellet. The KBr carrier method is preferred for small quantities of substance. As well as allowing qualitative determination of Mowiol, the IR spectrum also provides evidence of the degree of hydrolysis of the polymer. The two polymer grades shown below in the form of simplified structural formulas:
From these structures it is possible to derive the principle IR absorption bands: Fully hydrolysed Mowiol grades Atom grouping and type of oscillation Resonance absorption (wave number in cm1) 3 340 2 942 2 910 1 446 1 430 1 096 916 850 Intensity of the bands
OH stretching CH stretching CH stretching OH bending CH CH2 bending CO stretch and OH bending Skeletal
very strong strong strong strong strong strong medium medium
Partially hydrolysed Mowiol grades In addition to the above absorption bands there are also the characteristic bands for the ester grouping OCOCH3 :
Polyvinyl alcohol Partially hydrolysed H C O H Fully hydrolysed H C O H H C H H C O H H C H H C O H H C H H C O H H C H H C O H C H C O H C H CH3
Atom grouping C=O COC
Resonance absorption (wave number in cm1) 1 735 1 245
The intensity of these approximately equally strong absorptions provides information as to the degree of hydolysis of the polymer. The point is illustrated by the following IR spectra (Figure 4):
B8
The Mowiol Range
Degree of hydrolysis mol% 99
88
79
4 000
3500
3 000
2 500
2 000
1500
1000
500 cm1 Wave number
Figure 4 Characteristic IR spectra of Mowiol
B9
The Mowiol Range
B 5 Molar Mass and Degree of Polymerization of Mowiol

Polymers are identified, among other things, by their molar mass or degree of polymerization, the mean average weight Mw or Pw in relation to their molecule size. Because of the pronounced tendency to form associations, however, it is extremely laborious to measure molar masses on the polyvinyl alcohols themselves, and this frequently produces false results. Therefore the molar masses measured are often those of the polyvinyl acetates used to manufacture the polyvinyl alcohols, and from these values the molar masses of the polyvinyl alcohols themselves are calculated. To confirm the results the polyvinyl alcohols can be re-acetylized by methods known from the literature (eg in a pyridine/acetic anhydride mixture) and the resultant polyvinyl acetates re-analysed to determine their molar mass. In the case of polymers the molar mass values obtained always depend on the method of determination. Accordingly, comparisons are permissible only if the values have been obtained by the same methods under identical conditions. For the Mowiol grades listed in Table 3, the mean weights of the molar masses Mw were determined by gel permeation chromatography (GPC) combined with static light scattering (absolut method) on re-acetylized specimens. The accuracy of the Mw values was estimated at 15%.
The figures relate to a single production batch in each case.
For practical purposes an exact knowledge of the molar mass or the degree of polymerization is often only of secondary importance. For most applications it is quite sufficient to give the viscosity associated with these values for the (freshly produced) 4% aqueous solution and to know the degree of hydrolysis. The only crucial requirement is that, if different batches are involved, the molar mass or degree of polymerization for each grade should remain constant within the permitted tolerance; in the case of Mowiol this is ensured by use of the continuous production process.
Table 3
Molar mass Mw and degree of polymerization Pw of Mowiol grades Mw (g/mol) Pw 1900 270 630 750 1400 2700 3100 3300 4200 3700 360 600 1000 1400 2800 4300 3300
Partially hydrolysed grades
Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol
15-79 3-83 4-88 5-88 8-88 18-88 23-88 26-88 40-88 47-88 30-92 3-98 4-98 6-98 10-98 20-98 56-98 28-99
100 000 14 000 31 000 37 000 67 000 130 000 150 000 160 000 205 000 175 000 16 000 27 000 47 000 61 000 125 000 195 000 145 000
The degree of polymerization Pw is calculated by the following formula: Mw Pw = (86 0.42 degree of hydolysis)
Fully hydrolysed grades
B 10
Water is the most commonly used and technically most important solvent for polyvinyl alcohol. The dissolving procedure is simple, especially for Mowiol granules. The photograph shows starting product, dissolving procedure and solution.
Production of Mowiol Solutions Page
1 2 2.1 2.2 2.3 3 4
Solubility of Mowiol Determination of the relative Rate of Dissolution of Mowiol Partially hydrolysed Mowiol Grades Fully hydrolysed Mowiol Grades Rate of Dissolution of Mowiol Grades Industrial Production of Mowiol Solutions Other Solvents and Diluents for Mowiol
C1 C1 C1+ C2C6 C 1 + C 7 C 10 C 1 + C 2 C 10 C 11 C 11
C 1 Solubility of Mowiol
Water is the most common solvent for polyvinyl alcohol and, for practical applications, the most important. The solubility of Mowiol in water can be defined as the quantity of Mowiol which dissolves at a certain temperature in a given time in comparable apparatus (dissolving curve). It is natural feature of polymers that the production of a saturated solution is impossible, as for each grade an increase in concentration is accompanied by a rise in solution viscosity, the limit to which is set by that solution's industrial processability (see Section D 2).
Literature A Harrus, W Zimmermann, Hoechst AG/Resin News 19, 24 (1983)
Towards the end of the dissolving process a visual check must be made to determine clarity, specks and freedom from lumps. To determine further aspects of the various Mowiol grades' dissolving properties, this process can also be used at temperatures below 90 C (eg at 60, 40 and 20 C). As a general rule, a fall in the degree of polymerization and hydrolysis is accompanied by a rise in the rate of dissolution in water, as is clearly evident at different dissolving temperatures. In fully hydrolysed polyvinyl alcohols the effect of the degree of polymerization is generally more pronounced than in partially hydrolysed ones. Polymers whose level of hydrolysis is below 88 % are more soluble in water at low temperatures than at high temperatures.
C 2.1
Partially hydrolysed Mowiol Grades
C 2 Determination of the relative Rate of Dissolution of Mowiol

The relative rate of dissolution of Mowiol can be determined in the laboratory equipment described below: 180 g of deionized water at about 20 C is poured into a 500 ml three-necked flask fitted with a reflux condenser and impeller stirrer. 20 g of the Mowiol to be tested are sprinkled through a powder funnel during stirring (manual operation of the agitator used). The weight of volatile constituents must be taken into account. When the filling process is completed, the flask is placed in a thermostatically controlled water bath and the contents are stirred at about 250 min1. The start of agitation is taken as the zero point of the dissolving-time measurement. Experience shows that the water bath has to be heated to 95 99 C to give the required temperature of 90 C in the dissolver. The latter temperature is reached in a few minutes. 10 % solutions are produced to standardize the experiments. Because the diffusion of the water molecules in solvation is relatively slow and heavily dependent on viscosity, higher concentrations naturally require longer dissolving times. Every five minutes, one drop of the solution is removed by capillary pipette and used to determine the solution concentration by refractometry (see Section D 2.1). From these values the dissolving characteristics of a Mowiol grade can be plotted on the relevant concentration/time graph.
Figures 1 to 11 show the rate of dissolution and dissolving properties of partially hydrolysed Mowiol grades, measured by the method described in Section C 2. In the case of low-viscosity Mowiol 4-88 the graph shows that at 20 C after a sufficient time (30 min in the test) approx 96 % of the polymer has gone into solution. The still undissolved components are in the form of highly swollen, soft particles (lumps) which are very difficult to remove from the solution by filtration. At about 90 C, however, they dissolve without trace. It is also possible to separate out the lumps by decanting or centrifuging. Mowiol grades with a high residual acetyl content show different dissolving behaviour (cloud point).
C 2.2
Fully hydrolysed Mowiol Grades
Figures 12 to 19 show how important it is to maintain the dissolving temperature of 90 C, especially in dissolving the fully hydrolysed Mowiol grades. The dissolving curves show that in the temperature range 40 60C the granules do start to swell but scarcely dissolve at all. Only when this temperature is exceeded are they likely to dissolve properly. Completely clear and speck-free solutions are finally obtained at 90 C.
C 2.3
Rate of Dissolution of Mowiol Grades
Figures 1 to 18 on the following pages refer to the production of solutions with a target concentration in water of 10%. In each case the values were measured on a single batch.
C1
% Dissolved substance 100 90 80 70 60 50 90 C 60 C 40 20 C 30 20 10 0 5 10 15 20 25 30 35 40 45
Mowiol 15-79
min Dissolving time
Figure 1 Rate of dissolution of Mowiol 15 79
% Dissolved substance 100 90 C 60 C 90 40 C 80 20 C 70 60 50 40 30 20 10 0 5 10 15 20 25 30
Mowiol 3-83
min Dissolving time
C2
% Dissolved substance 100 90 C 90 60 C 80 70 40 C 60 20 C 50 40 30 20 10 0 5 10 15 20 25 30 35 40 45
Mowiol 4-88
min Dissolving time
% Dissolved substance 100 90 90 C 80 60 C 70 40 C 60 50 20 C 40 30 20 10 0 5 10 15 20 25 30 35 40 45
Mowiol 5-88
min Dissolving time
C3
% Dissolved substance 100 90 80 70 60 90 C
Mowiol 8-88
50 60 C 40 C 40 30 20 C 20 10 0 5 10 15 20 25 30 35 40 45 min Dissolving time
% Dissolved substance 100 90 80 70 60 50 90 C 40 60 C 30 20 40 C 10 20 C 0 5 10 15 20 25 30 35 40 45
Mowiol 18-88
min Dissolving time
C4
% Dissolved substance 100 90 80 70 60 50 90 C 40 60 C 40 C 30 20 C 20 10 0 5 10 15 20 25 30 35 40 45
Mowiol 23-88
min Dissolving time
% Dissolved substance 100 90 80 70 60 50 40 90 C 30 60 C 40 C 20 20 C 10 0 5 10 15 20 25 30 35 40 45
Mowiol 26-88
min Dissolving time
C5
% Dissolved substance 100 90 80 70 60 50 40 90 C 30 60 C 20 40 C 10 20 C 0

Figure 9
Mowiol 40-88
10
15
20
25
30
35
40
45
min Dissolving time
Rate of dissolution of Mowiol 40 88
% Dissolved substance 100 90 80 70 60 50 40 30 90 C
Mowiol 47-88
60 C 40 C 20 20 C 10 0 5 10 15 20 25 30 35 40 45 min Dissolving time
C6
% Dissolved substance 100 90 80 70 60 50 90 C 40 60 C 30 40 C 20 20 C 10 0 5 10 15 20 25 30 35 40 45
Mowiol 30-92
min Dissolving time
% Dissolved substance 100 90 90 C 80 70 60 C 60 50 40 30 20 10 20 C 0 5 10 15 20 25 30 35 40 45
Mowiol 3-98
min Dissolving time
C7
% Dissolved substance 100 90 C 90 80 70 60 50 40 30 20 10 40 C 20 C 0 5 10 15 20 25 30 35 40 45 60 C
Mowiol 4-98
min Dissolving time
% Dissolved substance 100 90 90 C 80 70 60 60 C 50 40 30 20 10 0 20 C 5 10 15 20 25 30 35 40 45
Mowiol 6-98
min Dissolving time
C8
% Dissolved substance 100 90 80 70 60 50 40 30 20 60 C 10 40 C 20 C 0 5 90 C
Mowiol 10-98
10
15
20
25
30
35
40
45
min Dissolving time
% Dissolved substance 100 90 80 70 60 50 40 30 20 10 60 C 40 C 20 C 0 5 90 C
Mowiol 20-98
10
15
20
25
30
35
40
45
min Dissolving time
C9
% Dissolved substance 100 90 80 70 60 50 90 C 40 30 20 10 60 C 40 C 20 C 0 5
Mowiol 56-98
10
15
20
25
30
35
40
45
min Dissolving time
% Dissolved substance 100 90 80 70 60 50 90 C 40 30 20 10 60 C 40 C 20 C 0 5
Mowiol 28-99
10
15
20
25
30
35
40
45
min Dissolving time
C 10
C 3 Industrial Production of Mowiol Solutions

Mowiol is usually processed in the form of its aqueous solution. Particular attention must therefore be paid to the way that this solution is produced. Stainless steel vessels, enamelled containers or polyester tanks should always be used as Mowiol solutions tend to be slightly acid. Mowiol is supplied in the form of granules. This ensures that no lumps develop when the hydrophilic polymer is sprinkled into the water. The temperature of the water used should not exceed 20 25 C, particularly for dissolving the partially hydrolysed Mowiol grades. The addition of defoamer (see Section D 4.1) prevents the formation of foam during the dissolving process. In practice two dissolving methods can be used: a. The use of directly heated dissolving vessels In this case the weighed quantity of Mowiol is sprinkled into the measured volume of cold water, which is agitated at the same time. The agitation process should be vigorous so as to dislodge the Mowiol particles settling on the bottom of the vessel, but it should not be so fast as to cause foaming. The suspension is heated while being continuously stirred. The contents of the vessel should reach a temperature of at least 90C as quickly as possible. At this temperature the Mowiol grades dissolve completely in a maximum of about 45 minutes (see Section C 2.1, C 2.2 and C 2.3). b. Injection of steam into a suspension of Mowiol granules The injection of live steam into a Mowiol suspension is a useful and quick method of dissolving Mowiol. The Mowiol is sprinkled into a small proportion of the calculated quantity of water for dissolving it while this is agitated vigorously, and live steam at a temperature of 110 140 C is then introduced. Some of the steam condenses. The weight or volume of water needed to adjust the solution to the desired concentration is determined at the end of the dissolving process and this quantity is then added. As with other polymers, no exact dissolving time can be given for Mowiol, as it depends mainly on the intensity of agitation, temperature control, grade and particle size. In general the partially hydrolysed products dissolve more quickly than the fully hydrolysed ones. In both the partially and fully hydrolysed Mowiol grades the rate of dissolution also increases with a decline in molecule size and a corresponding decrease in the viscosity of the aqueous solution (see also Section C 2). When Mowiol solutions are kept for longer periods, they must be stabilized with preservatives against attack by micro-organisms (see Section D 3.2).
C 4 Other Solvents and Diluents for Mowiol

Although in practice water is virtually the only solvent used for Mowiol, a number of other solvents or solvent mixtures suitable for Mowiol do exist. In this context we should refer not to good or poor solvents but to ones with a good or poor solvating power [1]. The dilution energy can be seen as a measure of the affinity between solvents and dissolved matter, although in polyvinyl alcohol this is complicated by its marked tendency which differs from case to case to form hydrogen bridges between the individual polymer chains and within the polymer chain itself. Huggins' empirical equation [2] describes a relationship between the solvation potential of a solvent and the rheological properties of the solution:
sp / c
= [ ] + K H [ ]2 c
The Huggins constant KH is a relative measure of the interaction between polymer and solvent, [ ] is the intrinsic viscosity ( sp / c for c 0) and c is the concentration of the solution. Thermodynamically, the smaller KH is, the greater is the dissolving power of a solvent for polyvinyl alcohol. For water, for example, KH is approx 0.75; and for an 85% phenol/water mixture it is about 0.4 [3]. The dissolving power of water/solvent mixtures may therefore be greater, for example, than that of pure water. With the exception of the phenol/ water mixture mentioned above, this is also true of water/alcohol mixtures, especially for the partially hydrolysed Mowiol grades. Certain polar solvents such as diethylene triamine [4], dimethyl sulphoxide [5], formamide, dimethyl formamide and phosphoric acid trisdimethylamide [6] are also relatively good solvents for Mowiol. At temperatures above 100 C, Mowiol can also be dissolved in multivalent alcohols such as glycerine, glycol and lower polyglycols, as well as in ethanolamines.
Literature [1] O Fuchs, Makromol. Chem. 18/19, 166 (1956) [2] M L Huggins, J. Amer. Chem. Soc. 64, 2716 (1942) [3] M Matsumoto, K Imai, J. Polym. Sci. 24, 125 (1957) [4] H C Haas, A S Makas, J. Polym. Sci. 46, 528 (1960) [5] R Naito, K Imai, Kobunshi Kagaku (Japan) 16, 217 (1959) [6] Hoechst Aktiengesellschaft, Ger. Federal Pat. 1 111 891
C 11
Solutions of polyvinyl alcohol exhibit viscosity. This product property depends among other things on the polymer type and the solution concentration. Viscosity is of importance to processing and to many uses of Mowiol.
Properties of Mowiol Solutions Page
1 2 2. 1 2. 2 3 3.1 3.2 4 4.1 4.1.1 5 6 6.1 6.1.1 6.1.2 6.2. 7 7.1 7.2 7.2.1 7.2.2 7.2.3 7.2.4 7.2.5 7.2.6 7.2.6.1 7.2.6.2 7.2.7 7.3
Viscosity / Concentration / Temperature Concentration of Mowiol Solutions Refractive Index and Concentration Density and Concentration Stability of Mowiol Solutions in Storage Increase in Viscosity through Association Preservation Interfacial Properties of Mowiol Solutions Defoaming of Mowiol Solutions Special defoamers Electrical Conductivity of Mowiol Solutions Additives affecting Viscosity Additives which reduce Viscosity Reducing the viscosity by desolvation Reducing viscosity by chain-splitting Additives which increase Viscosity Compatibility of Mowiol Solutions with water-soluble and water-dilutable Substances Salt Solutions (Electrolytes) Water-soluble Polymers Oxidatively degraded potato starch Oxidatively degraded potato starch, modified Oxidatively degraded corn starch Clariant polyglycols (polyethylene glycol) Casein Melamine and urea formaldehyde resins Melamine resins Urea resins Solutions of different Mowiol grades Polymer Emulsions
D 1 + D 2 D 11 D1 D 12 D 12 D 13 D 13 D 13 D 13 D 15 D 15 D 15 D 16 D 16 D 16 D 16 D 17 D 19 D 19 D 20 D 20 D 20 D 20 D 20 D 21 D 22 D 23 D 24 D 24 D 24
D 1 Viscosity / Concentration / Temperature

The viscosity of aqueous Mowiol solutions depends on the degree of polymerization and hydrolysis of the polymer, as well as on the concentration and temperature. For any given degree of polymerization, fully hydrolysed polyvinyl alcohols produce solutions with a higher viscosity than do partially hydrolysed ones. The polarity of the polyvinyl alcohol building blocks also causes association phenomena. These occur particularly in the higher concentration range of fully hydrolysed, high- and low-molecular Mowiol grades (see Section D 3.1). This (time dependent) orientation of the molecule chains before viscosity measurement, may distort the measured results. Viscosity measurements should therefore always be carried out on freshly produced, homogenous solutions adjusted to 20 C. Figures 1 and 2 show the concentration dependence of the viscosity of Mowiol solutions and Figures 3 to 20 its temperature dependence. The viscosity measurements were conducted in a Hppler fallingball viscometer as specified in DIN 53 015. In principle any other method of measurement produces comparable results. The specification of the Mowiol grades requires the viscosity of the 4% aqueous solutions at 20 C to be guaranteed within the range given in Section B 1, Table 1. It can be seen from the graphs that the relationship between viscosity and concentration and that between viscosity and temperature are non-linear and tend to be logarithmic. Viscosity curves for several batches of any specific Mowiol grade display a concentration- and temperature-dependent spread in their values. The range increases with the viscosity.
D 2 Concentration of Mowiol Solutions

Theoretically, solutions of any concentration can be prepared with Mowiol; for example, when a Mowiol film is cast from dilute aqueous solution, the solution passes through all concentration stages, until finally solidifying (100% solids). Mowiol solutions can be prepared in any concentration or diluted with water. However, because the viscosity of the solution rises very rapidly with the solid content, certain maximum concentration values must not be exceeded in practice. If the upper limit of viscosity at which the solution is still just processable is set at some 10 000 mPa s, the approximate upper concentration limits for the partially hydrolysed Mowiol grades are as follows: Mowiol 15 79: 18 % Mowiol 3 83: 40 % Mowiol 4 88: 30 % Mowiol 5 88: 28 % Mowiol 8 88: 25 % Mowiol 18 88: 16 % Mowiol 23 88: 15 % Mowiol 26 88: 15 % Mowiol 40 88: 12 % Mowiol 47 88: 12 % Mowiol 30 92: 13 % If the solution stands for some time at room temperature or below, the viscosity will increase and gelling may occur (see Section D 3.1). Solutions of fully hydrolysed Mowiol grades at high concentrations also tend to increase in viscosity and possibly to gel when left standing for long periods. In practice, therefore, stock solutions should be processed without delay and the following approximate maximum concentrations should not be exceeded: Mowiol 3 98: 30 % Mowiol 4 98: 25 % Mowiol 6 98: 25 % Mowiol 10 98: 20 % Mowiol 20 98: 15 % Mowiol 56 98: 12 % Mowiol 28 99: 12 %
Literature A Harrus, W Zimmermann, Hoechst AG/Resin News 19, 24 (1983)
D1
Partially hydrolysed grades mPa . s Viscosity at 20 C 10 000

9 10 11 8 7 6 1 5 4 3

6 7 5 4 3 2
1000
100
1 2 3 4 5 6 7 8 9 10 11 Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol 15-79 3-83 4-88 5-88 8-88 18-88 23-88 26-88 40-88 47-88 30-92
10
1 2 3 4 5 6 7
Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol Mowiol
3-98 4-98 6-98 10-98 20-98 56-98 28-99
1 0 10 20 30 % 0 10 20 30 % Concentration
Figures 1 and 2
Viscosity of Mowiol solutions as a function of concentration
D2
mPa . s Viscosity 100 000
Mowiol 15-79
Mowiol 3-83
10 000
20 %
10 000
40 %
15 % 1000 1000 30 %
10 % 100 100 20 %
10
5% 4%
10
10 %
2%
5% 4% 1
1 0 10 20 30 40 50 60 70 80 C Temperature
10 20 30 40 50 60 70 80 C Temperature
Figure 3 Viscosity as a function of temperature for Mowiol 15 79 solutions at different concentrations
D3
Mowiol 4- 88
Mowiol 5-88
10 000
32 % 30 %
10 000
25 % 1000 20 % 1000
25 %
20 %
15 % 100 10 % 100
15 %
10 %
10
5% 4%
10
5% 4% 2%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D4
Mowiol 8-88
Mowiol 18-88
25 % 10 000 10 000
18 %
15 % 20 %
1000
15 %
1000
10 %
100
10 %
100 5%
5% 10 4% 10
4%
2% 2%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D5
Mowiol 23-88
Mowiol 26-88
16 % 10 000 15 % 10 000
15 %
10 % 1000 10 % 1000
100 5% 4% 10 2%
100 5% 4%
10
2%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D6
Mowiol 40-88
Mowiol 47-88
14 % 10 000 12 % 10 000
13 %
10 % 10 % 1000 1000
100
5% 4%
100
5% 4%
2% 10 10
2%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D7
Mowiol 30-92
Mowiol 3-98
15 % 10 000 10 000
10 %
1000
1000
20 % 100 5% 4% 100 15 %
10 % 10 2% 10 5% 4%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D8
Mowiol 4-98
Mowiol 6-98
10 000
30 %
10 000
25 %
1000
25% 20 % 15 %
1000
20 %
15 % 100
100 10 %
10 %
10
5% 4% 2%
10
5%
4% 2%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D9
Mowiol 10-98
Mowiol 20-98
22 % 10 000 20 % 10 000
16 % 15 %
15 % 1000 1000
10 %
10 % 100 100 5% 5% 4% 10 2% 10 2% 4%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D 10
Mowiol 56-98
Mowiol 28-99
12 % 10 000 10 % 10 000
15 %
10 % 1000 1000
5%
100
4%
100
5% 4%
2% 10 10 2%
1 0 10 20 30 40 50 60 70 80 C Temperature
1 0 10 20 30 40 50 60 70 80 C Temperature
D 11
D 2.1
Refractive Index and Concentration
D 2.2
Density and Concentration
The concentration of a Mowiol solution can be found without product loss by measuring the refractive index in an Abb refractometer. As shown in Figure 21, the refractive index n20 rises in a straight D line with the Mowiol concentration between 0 and 30 wt.%. Series of tests with various Mowiol grades have shown that the refractive index is not dependent on the degree of polymerization. Likewise, refractometry reveals no difference between partially and fully hydrolysed Mowiol grades in aqueous solution.
The density of Mowiol solutions can be determined by the usual methods with an aerometer, Mohr balance or pycnometer, for instance (DIN 51 757). For continuous flow measurements on Mowiol solutions another suitable method is to use a density balance. As in the determination of the refractive index (see Section D 2.1), exact temperature control is also important for density measurement. Pycnometric density measurements on aqueous solutions of various Mowiol grades at 20 C (Figure 22) shows that, irrespective of the Mowiol grade, there is a linear relationship between density and concentration in the given range of concentrations between 0 and 20%.
n 20
D
Refractive index
1.38
g cm3 Density 1.05
1.37 1.04 1.36
1.03
1.35
1.02
1.34
1.01
1.00 1.33 0 5 10 15 20 25 30 % Concentration 0.99 0 5 10 15 20 % Concentration
Figure 21 Refractive index and concentration of aqueous Mowiol solutions The accuracy of the procedure depends mainly on the precision of the refractometer readings. Theoretically the absolute deviation n is 0.0001, corresponding to a difference in concentration c of 0.1 wt.%. The refractive index n20 of an anhydrous Mowiol grade is betD ween 1.52 and 1.53, depending on the degree of crystallization.
Figure 22 Density and concentration of aqueous Mowiol solutions
D 12
D 3 Stability of Mowiol Solutions in Storage

D 3.1 Increase in Viscosity through Association
D 3.2
Preservation
Like any other polyvinyl alcohol, Mowiol in aqueous solution can be attacked by micro-organism in certain circumstances. The acid pH range particularly encourages the multiplication of mould spores, whereas a neutral to weakly alkaline medium favours the growth of bacteria. Attack by micro-organisms can be prevented by the addition of a preservative. Examples of suitable preservatives are Mergal K 9 N and K 14 (a) or Kathon 886 (b) and Acticid SPX (c). The quantity required depends on the concentration of the solution, the storage temperature and the nature and intensity of the infection. Generally, concentrations of some 0.010.2% by weight of preservative relative to the Mowiol solution are sufficient. Information on the quantities to be used is provided by the manufacturers. It is advisable to prepare and store the Mowiol solutions in clean containers. In view of the possible resistance of some microorganism to the preservatives used, the dissolving vessel in particular, together with the filling equipment (pipework, valves, hoses, etc) should be kept clean. Skin and incrustations should be removed and the containers treated with dilute formaldehyde solution at regular intervals. If difficulties are encountered, consideration should also be given to changing the preservatives. Certain applications for Mowiol in solution (cosmetic preparations, finger paints, etc) require the use of approved, physiologically inert preservatives. The statutory requirements should always be observed in such cases.
(a) Riedel-de-Han, Seelze near Hannover (b) Rhom & Haas, Frankfurt (c) Thor-Chemie, Speyer Literature [1] M Matsumoto, Y Ohynagi, J. Polym. Sci. 26, 389 (1957) [2] T Matsuo, H Inagaki, Makromol. Chem. 53, 130 (1962) [3] K Amaya, R Fujishiro, Bull. Chem. Soc. Japan 29, 361 (1956) [4] K Amaya, R Fujishiro, Bull. Chem. Soc. Japan 29, 830 (1956) [5] H Maeda, T Kawai, S Seki, J. Polym. Sci. 35, 288 (1959)
In lengthy storage aqueous solutions of polyvinyl alcohols tend to undergo a reversible increase in viscosity which can result in gelling of the solutions. This phenomenon is the consequence of a defined polymer structure and attributable to gradual diffusion-controlled association of the dissolved polymer chains. The process can be observed in particular in concentrated solutions of fully hydrolysed PVAL grades. It may be described as follows: According to the literature [1], at time t the viscosity t is
t = o (1 +
c2),
where o is the initial viscosity, c is the concentration of the aqueous solution and is a product-related constant which depends on the method of manufacture of the polyvinyl alcohol concerned and thus on the respective chain structure. In studies into Mowiol 28-99 in 12% aqueous solution a constant increase in viscosity is found to occur within 43 days at 23 C from 2700 to 3600 mPa s for Mowiol 28-99. Using light-scattering measurements it is also possible to follow quantitatively the time-dependent changes in a PVAL solution [2]. The association of polymer chains responsable for the increase in viscosity is accompanied by desolvation of the macromolecules. Measurement of the heat of dilution on polyvinyl alcohol solutions accordingly produces lower values than would be expected in theory with solvation of all the hydroxyl groups of the polymer [3,4]. The non-solvated component exists in associated form [5]. An increase in the viscosity of Mowiol solutions can be reversed by heating during stirring. It is of practical significance here that the associates are not necessarily destroyed by merely diluting a thickened Mowiol solution with water. This fact has to be taken into account in storing and checking Mowiol stock solutions. Exact measurements of the viscosity of PVAL solutions should therefore not be conducted on dilutions of high-concentration stock solutions which have been stored for some time.
D 4 Interfacial Properties of Mowiol Solutions

Mowiol reduces interfacial tension, particularly the surface tension of water with respect to air. The different Mowiol grades produce different effects according to the viscosity, degree of hydrolysis and concentration in the aqueous solution.
D 13
mN . m 1 Surface tension 70
60
50 Mowiol 15-79 Mowiol 3-83 0 0,1 0,25 0,5 1,0 % Concentration
40 mN . m 1 Surface tension 70
60 Mowiol 30-92 Mowiol 40-88 Mowiol 18-88 Mowiol 8-88 Mowiol 4-88 0 0,1 0,25 0,5 1,0 % Concentration
50
40
mN . m 1 Surface tension 70
60
50
Mowiol 28-99 Mowiol 6-98 Mowiol 20-98 Mowiol 3-98 Mowiol 10-98 Mowiol 4-98
40 0
Figures 23 25
0,1
0,25
0,5
1,0
% Concentration
Surface tension of dilute Mowiol solutions as determined by a technique based on DIN 53 593
D 14
In the concentration range between approx 0.1 and 1% the surface tension of the water is generally reduced more in solutions of the partially hydrolysed Mowiol grades than in those of the fully hydrolysed grades (Figures 2325). This also explains the preference for partially hydrolysed grades as emulsifier/protective colloid. The differences in the relationship between surface tension and concentration in both the fully and the partially hydrolysed ranges can be explained only by differences in the molecular structure of the polyvinyl alcohol molecule. As the diagrams show, even traces of Mowiol lower the surface tension of water very substantially. The measurements on which the graphs were based were again obtained from a single production batch in each case. Variations in the values obtained must therefore be put into consideration. A similar situation exists in respect of the interfacial tension between Mowiol solutions and vinyl acetate, for example. The scatter observed in this case is relatively large and due partly to a change in the measured values over a period of time. For solutions of partially hydrolysed Mowiol grades and vinyl acetate the average measured values are 15 10mN m 1.
The quantity required depends on the concentration of the Mowiol solution and its further processing. Generally 0.001 to about 0.1% by weight of defoamer relative to the solution is sufficient. The defoamer is introduced immediately after the Mowiol granules are added to the water. A small quantity of defoamer may be added later after the dissolving process, but care must be taken not to add too much (deterioration in adhesion of Mowiol films, separation of the defoamer, etc).
D 4.1.1 Special defoamers

Most of the familiar, effective defoamers produce cloudy Mowiol solutions and films. In many applications this is unimportant. For completely clear Mowiol cast film a special defoamer has to be used, eg Agitan 290. Products of this kind must of course be compatible with the Mowiol solution, but are generally less effective than the defoamers generally used. If defoamed Mowiol comes into contact with foodstuffs, the defoamer incorporated in the polymer naturally has to comply with the statutory provisions as well. One example is the special product Agitan 305. The recommendations of the manufacturers should be followed.
(a) Mnzing-Chemie GmbH, Heilbronn (b) BASF, Ludwigshafen (c) Bayer AG, Leverkusen (d) Erbslh, Dsseldorf (e) Henkel KGaA, Dsseldorf
D 4.1
Defoaming of Mowiol Solutions
Traces of Mowiol lower the surface tension of water substantially (see Section D 4). Foaming can therefore be expected when aqueous Mowiol solutions are used. Even early on when these solutions are being prepared (see Section C 2 and C 3), the entrainment of air should be avoided by using suitable stirrers. All air should be excluded from any pipework through which Mowiol solutions are carried. The tendency to foam is more marked in partially hydrolysed than in fully hydrolysed Mowiol grades. The structure of the foam depends on the viscosity of the Mowiol solution. High-viscosity solutions give a relatively stable foam of a stiff, creamy consistency (see Section G 2.3). As the viscosity decreases the structure of the foam becomes coarser and unstable. Many substances are available for foam inhibition and defoaming. Those suitable for Mowiol include Agitan (a), Etingal (b), Bayer Defoamer (c), Bevaloid (d), Henkel defoamers (e) and higher alcohols, eg n-octanol. Agitan 290, 281, 305 and 731 as well as Bevaloid 6244 have proved particularly effective.
D 5 Electrical Conductivity of Mowiol Solutions

Mowiol is a non- electrolyte. However, because of the slight salt content of the polymer, some electrical conductivity exists in the aqueous solution. For 10% solutions it is of the order of K = 0.1 to 0.7 mS cm 1, corresponding to a specific resistivity of some 10 0001400 cm. These figures are only approximate and depend on the ash content. Products with an ash content of 0.5% by weight in a 10% solution have an electrical conductivity K of less than 1 mS cm1 (corresponding to a resistivity of 1000 cm).
D 15
Table 1
Effect of addition of electrolyte on the specific conductivity of 10% solutions of Mowiol 28 99 Added electrolyte Conductivity K (mS cm1) approx 0,52 11 9,9 7,7 5,3 2,5 0,003 Resistivity ( cm) approx 1 900 90 100 130 190 400 330 000
10 % solution of Mowiol 28-99
(no additive) + 5 % by weight MgCl2 + 5 % by weight NH4Cl + 5 % by weight NaCI + 5 % by weight NaNO3 + 5 % by weight (C2H5)4 NCI
De-ionized water Higher polymer conductivity is required for many Mowiol applications, one example being the special surface coatings for paper that has to dissipate electrostatic charges quickly. In such a case the addition of suitable electrolytes is recommended. Mowiol solutions have adequate compatibility with salts such as magnesium chloride, ammonium chloride, sodium chloride, sodium nitrate and quaternary ammonium compounds. Table 1 shows that even the addition of 5 % by weight of salt (relative to Mowiol) to a 10 % solution of Mowiol 2899, for instance, sometimes increases the specific conductivity by more than one order of magnitude. The electrical values of Mowiol films are also affected correspondingly. The measurements where conducted at 25C/200 Hz. The values do not change much if the frequency is increased to 2 kHz.
stripped from the polyvinyl alcohol that solvation of the polymer is no longer adequately assured. The viscosity of the polymer solution then begins to rise again and finally the polyvinyl alcohol flocculates. Solvation is also highly temperature-dependent. Relatively high temperatures can lead to reversible flocculation and clouding of the solution. Examples of compounds which can reduce the viscosity of Mowiol solutions in accordance with the above criteria are magnesium chloride, urea, tetraethyl ammonium chloride, sodium fluoborate, calcium chloride and calcium rhodanide.
Literature [1] H Schindler, Hoechst AG/Resin News 13,4 (1978) [2] S Peter, H Fasbender, Koll-Ztschr. 188, 14 (1962)
D 6 Additives affecting Viscosity

The viscosity of Mowiol solutions of certain concentrations can be affected by introducing additives [1]. Depending on their physical/chemical action these can either increase or reduce the viscosity.
D 6.1.2 Reducing viscosity by chain-splitting Another possibility for reducing the viscosity of Mowiol solutions consists in the oxidative breakdown of the polymer chains. Under mild conditions the polymer chains of PVAL are split with even only small quantities of periodate. This may be a reaction at 1,2 glycol units of the polyvinyl alcohol chain (see Section A 3.1) [1]. This reduction in viscosity is illustrated for Mowiol 488 in different concentrations in Figure 26. The reaction takes place virtually spontaneously even at room temperature. Breakdown of the Mowiol chains with other oxidizing agents, eg peroxides, is possible only under much more severe test conditions [2,3]. The quantities of peroxide needed to achieve a given viscosity and the reaction conditions have to be determined individually for each case in a preliminary test.
D 6.1
Additives which reduce Viscosity
D 6.1.1 Reducing the viscosity by desolvation Thermodynamically the viscosity of Mowiol solutions is determined by the solvation of the dissolved macromolecules. There have been found to be some 84 to 99 bound molecules of water per basic building block of vinyl alcohol [2]. This immobilization of water molecules is ultimately responsible for the flow behaviour of Mowiol solutions and its temperature-dependence (see Section D 1). By using highly polar, hygroscopic, neutral compounds which are chemically inert to polyvinyl alcohol it is possible to remove water molecules from the polyvinyl alcohol building block and thus reduce the viscosity of a Mowiol solution. The limit to this method is reached when so many water molecules have been
Literature [1] H F Harris, J G Pritchard, J. Polym. Sci., A 2, 3673 (1964) [2] Consortium fr Elektrochemische Industrie GmbH, DRP 747 879 [3] H Shiraishi, H Matsumoto, Kobunshi Kagaku (Japan) 19, 722 (1962)
D 16
Boric acid gives the monodiol complex:
mPa . s Viscosity 1000 1 2 3 4 no additive + 1 % NaIO4 + 3 % NaIO4 + 5 % NaIO4
Mowiol 4-88 H2C 1 2 3 4 H2C

Polyvinyl alcohol / boric acid monodiol complex
HC H2C HC
O B O OH
100
10
The viscosity of solutions of these monodiol complexes depends mainly on the chain length and degree of hydrolysis of the polyvinyl alcohol used [2].
0 2 4 6 8 10 12 14 16 18 20 % Concentration
Different behaviour is found in a Mowiol solution under the action of borates or a Mowiol solution containing boric acid where the pH is shifted to alkaline. The polyvinyl alcohol/boric acid monodiol complex forms, as polyelectrolyte, the polyvinyl alcohol/boric acid didiol complex, in which two polyvinyl alcohol chains are interlinked via boric acid [3, 4]. Recently, structures with ionic bonds have also been suggested in this case [5].
Figure 26 Change in the viscosity of a Mowiol 4 88 solution when NaIO4 is added
H2C HC H2C HC H2C D 6.2 Additives which increase Viscosity O O
Na+ O () B O CH CH
CH2 CH2 CH2
The regularly arranged hydroxyl groups of the polyvinyl alcohol chain are capable of forming chemically more or less stable complex compounds or associates with certain substances, and these cause an increase in viscosity or even gelling of the polyvinyl alcohol solution, depending on the concentration of the admixture. In special cases the addition of one of these complex forming substances to the Mowiol solution also leads to other effects of practical value. The classic example of complex formation with polyvinyl alcohol is its reaction with boric acid on the one hand and borates on the other [1].
Polyvinyl alcohol / boric acid didiol complex
Figure 27 shows the viscosity of 4 % Mowiol solutions after the addition of boric acid for three Mowiol grades with different pH values. The values found are highly temperature- and timedependent. Mowiol is precipitated by borax solution even at relatively high dilutions. The reaction of the monodiol complex with iodine forms the basis of a sensitive detection method for polyvinyl alcohol [6, 7, 8].
D 17
In practical applications the addition of boric acid to Mowiol solutions brings about a substantial increase in wet adhesive strength in adhesives.
mPa . s Viscosity 100 gelled gelled
The viscosity of Mowiol solutions can be raised not only with boric acid and its salts but also with complex-forming compounds of the elements of sub-groups IV to VI of the periodic system. In certain circumstances this increase in viscosity causes the solution to gel. In many cases the complex which forms can be thermally fixed. This provides a practicable method of tanning a Mowiol layer, ie a method of making the Mowiol film insoluble. As one example, the titanium-IV-triethanolamine complex used with polyvinyl alcohol solution produces highly viscous to gelling titanium-IV complexes [9, 10]. The increase in viscosity produced by this complex is largely independent of pH. Titanium sulphate also reacts in a similar way with polyvinyl alcohol solution [11]:
Mowiol 28-99
Mowiol 4-88
gelled
CH2 Mowiol 4-98 10 CH O Ti O

Titanium-IV / polyvinyl alcohol complex
CH O
Titanium-III, vanadium and chromium compounds cause gelling of the Mowiol solution even at low concentrations. Organic compounds can likewise lead to an increase in the viscosity of Mowiol solutions. The acetalyzation of polyvinyl alcohol, eg with formaldehyde and acid (as catalyst) should also be mentioned. Small quantities of such substances produce thickening and even gelling of the Mowiol solution. Stopping the acetalyzation reaction with caustic solution fixes the consistency reached in the mixture. This method of increasing the viscosity is used industrially (see Section G 1.10, for example). Relatively loose complexes (associates) in Mowiol solutions are formed by the action of direct dyes, eg Congo red [12]. Even small quantities produce a marked increase in the viscosity of the Mowiol solution. The colouring imparted to the solution and any toxicity of the dyes are factors to take into account in any decision to use such additives. These associates are thermally reversible, ie it is possible to produce Mowiol-Congo red gels which become liquid at elevated temperature.
1 0 2 4 6 8 10 pH
Figure 27 Viscosity of 4% aqueous Mowiol solutions as a function of pH after the addition of boric acid (5 % boric acid relative to Mowiol, 20 C, dwell time 5 minutes)
D 18
Polyvalent phenols and related compounds such as resorcinol, pyrocatechol, phloroglucinol, gallic acid, salicylic anilide and 2,4-dihydroxybenzoic acid behave in a similar way, although their action is not as powerful as that of Congo red.
stances with Mowiol in solution. Preliminary tests are always advisable. The following sections should therefore be regarded merely as a survey of various classes of substance, the details being intended only for general guidance.
D 7.1
Literature IG Farbenindustrie AG, DRP 606 440 T Motoyama, S Okamura, Kobunshi Kagaku 11, 23 (1954) S Saito et al, Koll. Ztschr. 144, 41 (1955) H Deuel, H Neukom, Makromol. Chem. 3, 137 (1949) M Shibayama, H Yoshizawa, H Kurokawa, H Fujiwara, S Nomura, Polymer 29, 2066 (1988) W O Herrmann, W Haehnel, H Staudinger, K Frey, W Starck, Ber. Dtsch. Chem. Ges. 60, 1782 (1927) [7] IG Farbenindustrie AG., DRP 731 091 [8] M M Zwick, J Appl. Polymer Sci, 9, 2393 (1965) [9] E Eld, T Schachowsky, Kolloid Beihefte 51, vols 14, 111 (1940) [10] DuPont, U.S.Pat. 2720 468 (1955) [11] DuPont, U.S.Pat. 2518 193 (1950) [12] Chem. Forschungsges. mbH, DRP 686 123 [1 [2] [3] [4] [5] [6]
Salt Solutions (Electrolytes)
As described in Section D 5, Mowiol is a non-electrolyte. Aqueous solutions and films cast from them exhibit no particular electrical conductivity. For many applications, however, the addition of an electrolyte to Mowiol may be beneficial (eg paper with an electrically conductive coating). Compatibility with salts therefore needs to be considered. As Table 1 shows (page D 16), compatibility depends not only on the cation but more especially on the anion. To obtain qualitative comparisons, 10 g of a salt solution is prepared and mixed vigorously with one drop of 10 % Mowiol solution. The values given in Table 2 represent the maximum salt concentrations that lead to incipient clouding of the mixture. The higher the concentration, the better the compatibility between Mowiol and electrolyte. The effect of the degrees of polymerization and hydrolysis on the electrolyte compatibility is not very pronounced. Polyvalent anions such as sulphate and carbonate ions should not be used in Mowiol solutions. Magnesium chloride and both ammonium and sodium nitrate are notable for their good compatibility with Mowiol grades. Salts of polyvalent acids, especially those in groups III, IV, V and VI of the periodic system, eg borates, titanates, vanadates and chromates, produce complexes with Mowiol in solution (increase in viscosity, flocculation). These salts are described separately in Section D 6.2, which considers their reactivity.
D 7 Compatibility of Mowiol Solutions with water-soluble and water-dilutable Substances

In practical applications Mowiol is often combined with other water-soluble or water-dilutable substances. For example, when Mowiol is used as a binder in the paper or glass fibre nonwovens industry, the addition of reactant resins based on phenol, melamine or urea formaldehyde can impart resistance to boiling to supplement the outstanding fibre/fibre binding power. Other applications require the formation of electrically conductive Mowiol films which can be produced by adding salts to the polymer solution. In the adhesive sector, special polymer emulsions are made up with Mowiol. For technical reasons, water-activated adhesives based on Mowiol are sometimes blended with polymer emulsions. The addition of Mowiol to other polymer products such as starches can improve their film-forming properties or adhesion to various substrates. The rules of macromolecular chemistry raise the question as to the compatibility of these water-soluble or water-dilutable sub-
Electrolyte NaCl K2SO4 (NH4)2SO4 NH4NO3 NaNO3 ZnSO4 CuSO4 Al2(SO4)3 Na 2S2O3 Na 2CO3 MgCl2 Table 2
Mowiol 4-88 % 18 4 6 30 25 4 8 4 7 5 30
Mowiol Mowiol Mowiol 40-88 4-98 28-99 15 4 3 30 23 5 5 4 6 5 30 18 4 7 30 29 5 12 5 8 6 30 16 3 5 29 24 5 8 5 6 5 30
Compatibility of various electrolytes with 10 % Mowiol solutions (incipient clouding where 1 drop of Mowiol solution is added to 10 g of salt solution)
D 19
D 7.2
Water-soluble Polymers
As a rule, solutions of two chemically different polymers in the same solvent in this case water are not mutually compatible (phase separation occurs immediately or after the mixture has been standing for some time). This also applies to solutions of Mowiol combined with those of substances such as starch, casein, polyethylene glycol and polyacrylamide, and even applies to combined solutions of fully and partially hydrolysed Mowiol grades. Compatibility can best be achieved by using one component in considerably smaller quantities than the other. Compatibility between components is usually poor if they are used in a ratio of 1:1.
D 7.2.2 Oxidatively degraded potato starch, modified with 2-hydroxy-n-propyl ether groups (OCH 2CH(OH)CH 3) Studies have shown that, as the level of substitution of the starch rises, its compatibility with Mowiol decreases. The starch with the lowest substitution level has the best compatibility although, as the molar mass of the Mowiol increases, phase separation may also occur. Mixtures in which one of the components greatly predominates behave best in this group also. Preliminary trials are necessary.
D 7.2.3 Oxidatively degraded corn starch D 7.2.1 Oxidatively degraded potato starch Unmodified potato starches of various degrees of degradation were used to assess the compatibility of oxidatively degraded potato starches with Mowiol. Studies were conducted on mixtures of 10% solutions of these starches with Mowiol solutions of equal concentration in the proportions 9 : 1, 8 : 2, 5 : 5, 2 : 8 and 1 : 9 at room temperature. Each solution was assessed immediately after mixing and again after standing for 24 hours. As the starch solutions are sometimes intrinsically cloudy or milky in appearance and affect the transparency of mixtures with Mowiol, due allowance for this has to be made in any assessment. The degree of degradation of the oxidatively treated potato starches affects miscibility. The best compatibility with Mowiol grades is displayed by the starch with the lowest level of degradation. Any reduction in the chain length of the starch increases the likelihood of incompatibility phenomena (from clouding to phase separation). Mixtures of equal parts of starch and Mowiol should be avoided if at all possible. In mixtures with heavily degraded starches the Mowiol component should always predominate. This principle applies in particular to partially hydrolysed Mowiol grades with increasing molecular weight. In practice, fillers are often added to the mixed Mowiol/starch solutions (eg in paper-coating compounds). These fillers are chemically inert towards the polymers, but the rate of adsorption of the various binders on the filler may vary, causing a shift in the concentration ratios with corresponding consequences. Preliminary trials are therefore essential. Like potato starch, corn starch is oxidatively degraded so that it can be converted into colloidal solutions. The combination of these starches with Mowiol produces technical advantages in many areas of application, and consequently information on the compatibility between these two polymers is called for. Starches with different levels of degradation were tested by the procedure described in Section D 7.2.1. The starches yield opaque to cludy solutions. Thus, after Mowiol is added, the only way to recognize incompatibility may be from the occurrence of phase separation. The best compatibility is found with low-viscosity partially hydrolysed Mowiol. Mixtures with medium- and high-viscosity Mowiol grades are more problematic. Here again, mixtures with a large Mowiol component are the best. The effect of the level of starch degradation cannot always be clearly seen, but in some cases the starch with the lowest molecular weight exhibits the best compatibility.
D 7.2.4 Clariant polyglycols (polyethylene glycol) Polyethylene glycols (PEG) with low molar mass can be used as plasticizers for Mowiol. The following tables list the degrees of compatibility between the two polymers both in aqueous solution and in film form after drying. To determine compatibility, 10% Mowiol solutions are prepared, one from a low-viscosity grade and one from a high-viscosity grade in the partially hydrolysed ranges and a further two solutions from equivalent grades in the fully hydrolysed ranges. PEG also in 10% solution is added in the percentages shown with respect to Mowiol (Table 3).
D 20
Table 3
Compatibility between Mowiol and PEG in aqueous solution, total solids content 10% Mowiol 4-88 Mowiol 40-88 Mowiol 4-98 Mowiol 28-99 40 20 10 1 1 1 2 2 2 2 2 2 2 5 1
Clariant polyglycols PEG grades 200 300 400 600 1500 3 000 6 000 10 000 20 000 35 000
40 20 10 1 1 1 1 2 2 2 2 2 2
Added percentage with respect to Mowiol 40 20 10 5 1 40 20 10 5 1 1 1 1 1 2 2 2 2 2 2 1 1 1 2 2 2 2 2 2 2
1 1 2 2 2 2
1 1 2 2
1 1 1
1 2 2 2 2 2
1 2 2 2 2
1 1 2 2
1 1
1 2 2 2 2 2 2
1 1 2 2 2 2
1 1 2 1 2 1
1 2 2 2 2 2 2
1 2 2 2 2 2
1 1 1 2 2
1 1
The results show relatively good compatibility between all Mowiol grades and polyglycols of low molar mass. Clear solutions are sometimes obtained even when 40% Clariant polyglycol 400 to 600 is added. For films cast from clear mixed solutions see Table 4. Clariant Mowiol polyglycols 4-88 PEG grades 200 300 400 600 1500 3 000 6 000 10 000 20 000 35 000 Table 4 > 40 > 40 > 40 > 40 < 10 < 5 < 1 < 1 Mowiol 40-88 <5 <1 <1 <1 <1 <1 Mowiol 4-98 > 40 < 20 < 5 < 1 Mowiol 28-99 > 40 < 10 < 10 < 5 < 1
1 = clear mixture; 2 = cloudy mixture (phase separation); blank spaces correspond to rating 1
Maximum PEG concentration in %
In practice, depending on the chain length of the Mowiol, PEG grades up to a maximum molar mass of 200 to 400 can be used to plasticize it. The proportion of plasticizer should not exceed 10 20% in order not to reduce Mowiol's excellent film strength too greatly. An excessive proportion of PEG may cause it to be exuded. D 7.2.5 Casein The rules for blending different polymers also apply to the combination of Mowiol and casein, ie perfect compatibility is not assured. Solutions of the two polymers mix relatively well when the mixture ratios are extreme values, eg 1 : 9 or 9 : 1. The compatibility is slightly better when Mowiol predominates than when the casein does. In mixtures of equal parts, compatibility is only slight or non-existent. With increasing polymer concentration in the solution, all mixtures exhibit decreasing compatibility. The time factor plays an important part in the assessment. In certain circumstances the incompatibility increases sharply after a lengthy standing time, eg 48 hours. In the investigations it was not found that the degree of polymerization or hydrolysis of the Mowiol grade used for the mixture had a great influence on the compatibility.
Compatibility of Mowiol and PEG in a cast film after 14 days' storage in a standard operating environment
The percentages give the maximum compatible proportions of various polyglycols added to the individual Mowiol grades. Here again a relationship exists between compatibility and the molar mass of the PEG used. The effect of the degree of hydrolysis and the chain length of Mowiol is also clearly evident. Compared with fully hydrolysed Mowiol, partially hydrolysed Mowiol grades of the same chain length can be blended with larger quantities of PEG. In addition, irrespective of the degree of hydrolysis of the Mowiol, the PEG compatibility increases sharply as the molar mass of the Mowiol decreases.
D 21
D 7.2.6 Melamine and urea formaldehyde resins During thermal curing, melamine and urea formaldehyde resins go through a brittle phase. This phenomenon can be avoided if Mowiol solution is added to the water-soluble precondensates. Small added quantities have scarcely any effect on the water resistance of the cured compounds. On the other hand, relatively small additions of urea resins or, more especially, melamine resins can substantially increase the water-resistance of Mowiol films. They also increase film hardness. Some applications require a certain maximum viscosity in the polymer solution. Blending Mowiol with the reactant resins has
the advantage that the solids content of the total mixture at any given viscosity can be increased while the viscosity remains virtually unchanged. This is possible because urea resins and especially melamine resins have relatively low viscosities in comparatively high concentrations. It should be noted that urea resins and melamine resins are usually alkaline to neutral, whereas the pH of Mowiol solutions is as a rule between < 5 and 7. The proportions of Mowiol and reactant resin in the mixture are chosen so that a neutral to slightly acid pH is obtained. This is necessary in order to achieve cross-linking between the polymers in a reasonable time at high temperature. On the other hand, excessive acidity limits the pot life of the mixture.
Table 5 Compatibility between partially hydrolysed Mowiol grades and melamine resin Madurit MW 3816 Mowiol 4-88 Total solids content of mixture 10 % 20 % pH 6,2 6,3 6,2 6,1 6,6 6,7 6,6 6,5 7,2 7,2 7,1 7,0 Rating 1 3 3 3 1 3 3 3 1 1 2 2 pH 6,0 6,1 6,1 6,0 6,5 6,6 6,5 6,4 7,1 7,2 7,1 7,0 Rating 1 3 3 3 1 1 3 4 1 1 1 1 pH 6,2 6,3 6,3 6,3 6,7 6,8 6,8 6,7 7,4 7,3 7,2 7,1 Mowiol 40-88 Total solids content of mixture 10 % 15 % Rating 1 3 3 3 1 2 3 4 1 1 1 2 pH 6,2 6,4 6,4 6,6 6,7 6,7 6,7 7,3 7,3 7,2 7,1 5 = gelled mixture Rating 1 3 3 5 1 1 3 3 1 1 1 1
Parts by weight Mowiol solution + Dwell Madurit MW 3816 time/ h 8+2 0 24 48 72 0 24 48 72 0 24 48 72
5+5
2+8
1 = clear mixture;
2 = opaque mixture;
3 = very cloudy mixture;
4 = phase separation in mixture;
D 22
D 7.2.6.1 Melamine resins Madurit MW 3816 Tables 5 and 6 show the results of extended compatibility tests on fully and partially hydrolysed Mowiol grades with the melamine resin Madurit 3816. Each of the tests was carried out with one low-viscosity and one high-viscosity Mowiol grade: Mowiol 488 and Mowiol 4088, and Mowiol 498 and Mowiol 2899.
A good compatibility with Madurit MW 3816 over the entire testing period was seen in the mixtures of the ratio 2 : 8 (all types of PVAL and in all concentrations). At a mixing ratio of 1 : 1 an intensive cloudy solution was observed after 24 to 48 hours. Whereas after 24 hours, the mixing ratio 8 : 2 resulted in clouded solutions and the 20% mixture 4088 was gelling after 72 hours (Tables 5 and 6). Along with Madurit MW 3816, there are three further melamine resins that are appropriate for mixing with Mowiol which have been tested. Ranging in success from the decreasing concentrations of formaldehyde they are Madurit SMW 818, MW 113 and MW 830. Madurit MW 113 can be compared with Madurit 3816. Retrospectively the melamine resins do not show large differences among themselfes during the whole testing period. Preliminary tests to determine compatibility are essential.
As a 10% and 20% solution Mowiol 488 was blended with a melamine resin of the same concentration. Mowiol 4088, 498 and Mowiol 2899 were blended as a 10% and 15% solution in ratios of 8 : 2, 5 : 5 and 2 : 8. Using a stirring apparatus, the blend was mixed and initially the solutions were clear.
Table 6
Compatibility between fully hydrolysed Mowiol grades and melamine resin Madurit 3816 Mowiol 4-98 Total solids content of mixture 10 % 15 % pH 6,4 6,6 6,6 6,5 7,0 7,0 7,0 6,9 7,6 7,6 7,4 7,4 Rating 1 3 3 3 1 1 3 3 1 1 1 1 pH 6,2 6,5 6,5 6,4 6,8 7,0 6,9 6,8 7,5 7,6 7,4 7,3 Rating 1 3 3 3 1 1 3 3 1 1 1 1 pH 6,6 6,8 6,8 6,7 7,2 7,3 7,2 7,1 7,8 7,8 7,6 7,5 Mowiol 28-99 Total solids content of mixture 10 % 15 % Rating 1 3 3 3 1 1 2 3 1 1 1 1 pH 6,4 6,7 6,7 6,6 7,0 7,2 7,1 7,0 7,7 7,7 7,6 7,4 5 = gelled mixture Rating 1 3 3 3 1 1 2 3 1 1 1 1
Parts by weight Mowiol solution + Dwell Madurit MW 3816 time/ h 8+2 0 24 48 72 0 24 48 72 0 24 48 72
5+5
2+8
1 = clear mixture;
2 = opaque mixture;
3 = very cloudy mixture;
4 = phase separation in mixture;
D 23
D 7.2.6.2
Urea resins
D 7.3
Polymer Emulsions
The results here are similar to those obtained in compatibility tests between Mowiol and melamine resins. High-viscosity partially hydrolysed grades in particular give the best compatibility, the total concentration being set as high as possible (15%). Where fully hydrolysed Mowiol grades are used in a mixture, a shorter pot life is generally likely. As with the melamine resins, one reaction component should greatly predominate in the mixture. Care must be taken to ensure an acid pH after mixing, especially with a high Mowiol component, as this helps condensation with the urea resin. At pH 67 a slight increase in pot life can be achieved.
Many polymer emulsions, especially polyvinyl acetate emulsions used in the glue and adhesives sector, contain Mowiol as protective colloid (see Section G 1.1.1). It can sometimes be an advantage for emulsions to be subsequently blended with Mowiol, eg to affect the viscosity or sensitivity to water. Modifying such emulsions with Mowiol solution can also have a beneficial effect on a number of technical properties such as the open time and initial grab (see Section G 1.3.2). In general any assessment of compatibility between emulsions and Mowiol solution must take account of the time factor. Incompatibility often cannot be established until the mixture has been standing for several hours. In the study of mixtures of Mowilith emulsions with Mowiol, no fundamental incompatibility has so far been found. Even emulsions containing cellulose, such as Mowilith DC approx 56 % or DC 02 approx 60 %, can be prepared in ratios by weight of 1 : 1 without flocculation occurring if, for example, 10% Mowiol solutions are used. It is essential for the Mowiol solution to be incorporated slowly while being stirred vigorously. The same applies to emulsifier-stabilized emulsions. Partially hydrolysed Mowiol grades are particularly suitable for blending with Mowilith emulsions. As any addition of Mowiol solution causes dilution of the emulsion, creaming or precipitation are likely when relatively large quantities are involved. This applies in particular to emulsions containing mainly single particles such as Mowilith DHS approx 50%. Precipitation does not indicate lack of compatibility between polymer solution and emulsion in this case but merely shows the need to keep these mixtures moving by pumping or stirring, so that uniform distribution of the emulsion particles is maintained.
D 7.2.7
Solutions of different Mowiol grades
Mowiol grades with the same degree of hydrolysis can be combined with one another in solution without restriction. However, when aqueous solutions of partially and fully hydrolysed Mowiol grades are intermixed, incompatibility phenomena can occur (cloudy solutions or films). It has been found that, if the acetyl content differs by only a few mol%, unrestricted compatibility no longer exists and a miscibility gap is likely. Mixture ratios around 1 : 1 are, of course, critical. In practice, when special viscosity settings are used, for example, it is therefore advisable to blend partially hydrolysed grades only with partially hydrolysed, or fully hydrolysed only with fully hydrolysed. If a combination of Mowiol grades of different degrees of hydrolysis cannot be avoided, the percentage of one component should heavily predominate (see Section G 1.2.1)
D 24
The Mowiol Film
From solution or from the melt, Mowiol forms clear, high-gloss, water-soluble films with high tear strength. The films are permeable to water vapour. Permeability to most gases is low.
The Mowiol Film Page
1 2 3 4 5 5.1 5.2 6
Water Absorption and Water Resistance of Mowiol Films Plasticizers Tear Strength and Elongation at Break of cast Mowiol Films Gas Permeability Solvent Resistance of Mowiol Films Water-miscible Solvents Water-immiscible Solvents Electrophysical Properties of Mowiol Films
E 1 E 3 E 3 E 5 E 5 E 5 E 5 E 5
The Mowiol Film
E 1 Water Absorption and Water Resistance of Mowiol Films

Although not hygroscopic, Mowiol films do absorb some moisture, the amount depending on the partial pressure of the water
vapour. This affects the properties of the film. The path of the moisture absorption curve for partially and fully hydrolysed Mowiol grades in relation to the relative humidity is shown in Figures 1 and 2. To measure water absorption, 0.3 mm films were cast from 10% aqueous solution from one Mowiol batch in each case, then dried in air at 23 C and 50% relative humidity. These films were
% Water content 15
4 3 1 2 5
10
1 2 3 4 5
4-88 8-88 18-88 26-88 40-88
5
1, 2, 5 4 3
20
40
60
80 Relative humidity at 23 C
100 %
Figure 1 Water absorption and relative humidity at 23 C for films of partially hydrolysed Mowiol grades
E1
The Mowiol Film
afterwards stored for 7 days at 23 C and various relative humidities between 15 and 92%. The water absorption or emission was measured by gravimetric weight analysis under comparable conditions. The results are based on approximate values. The pattern of the increase in water content with a rise in relative humidity is very similar for all grades, both partially hydrolysed (Figure 1) and fully hydrolysed (Figure 2). In general the fully hydrolysed films absorb slightly more water at low humidities than do the partially hydrolysed ones.
The water resistance of dried Mowiol films rises with increasing molar mass and the degree of hydrolysis. The water resistance of a Mowiol film can be increased even further by heat-treatment, eg drying at 120 C. Alternatively, acids, such as orthophosphoric acid, or salts, such as ammonium chloride or sodium / ammonium bichromate, can be added to the Mowiol solution, the added quantities being about 5% relative to the Mowiol. Aldehydes, eg formaldehyde or glyoxal and urea formaldehyde resin and melamine formaldehyde resin (see
% Water content 15
4 5 1 3 2
10
1 2 3 4 5
4-98 10-98 20-98 56-98 28-99
5 2, 3, 4 1
20
40
60
80
100 %
Relative humidity at 23 C
Figure 2 Water absorption and relative humidity at 23 C for films of fully hydrolysed Mowiol grades
E2
The Mowiol Film
Section D 7.2.6), in quantities of 10 20 % relative to the Mowiol, can also help increase the water resistance of cast films (see also Sections G 1.8 and G 2.2). UV irradiation of the dried Mowiol film is another method.
Literature H Schindler, W Zimmermann; Hoechst AG/Resin News 11, 26 (1976)
Another method of assessing a plasticizer's effectiveness is to determine the cloud point of Mowiol in the plasticizer concerned. This may be done, for example, by slowly cooling a 1% solution of the polymer in the plasticizer until cloudiness sets in, indicating the temperature at which the solvating power of the plasticizer ceases. The lower this temperature, the better is the plasticizing action of the plasticizer. For any specific type and quantity of plasticizer, the effectiveness is higher in partially hydrolysed Mowiol grades than in fully hydrolysed ones.
E 2 Plasticizers
Anhydrous Mowiol films are stiff and tough to relatively hard. These properties change with the chain length and degree of hydrolysis of the product. Hence, depending on the area of application and the grade of Mowiol used, the polymer may need to be plasticized. Plasticizers for polymer compounds have to satisfy various requirements: the compatibility must be so good that the plasticizer does not migrate out of the polymer film. Because of the numerous hydroxyl groups in the polymer chain, Mowiol has a polar character. Therefore, only compounds with highly polar hydrophilic groups can be used as plasticizers. The volatility of the plasticizer should also be as low as possible. Although water exerts a particularly marked plasticizing effect so that films stored in moist air become viscoplastic to soft, it cannot be considered an ideal plasticizer because of its high volatility. Plasticizers with a long-lasting action should have such low partial vapour pressure that volatilization will rarely, if ever, occur. The effectiveness of a plasticizer for Mowiol can be determined in various ways: Differential thermal analysis (DTA) provides information about the second-order transition point of Mowiol / plasticizer mixtures. The lower this temperature for any specific added quantity, the more effective is the plasticizing action. Measurement of the elongation at break and torsional vibration tests are customary on plasticized Mowiol films in particular.
The plasticizers used in practice are ethylene glycol, di- and triethylene glycol, PEG (up to molar masses of approx 400), glycerine, trimethylol propane, neopentyl glycol, triethanolamine, etc. There are also references in the literature to ethoxylated phosphates as suitable compounds. They are used in quantities of up to 30% relative to Mowiol.
E 3 Tear Strength and Elongation at Break of cast Mowiol Films

Under normal conditions Mowiol films, especially those of higherviscosity grades, have a high tear strength and good elongation at break. These properties are affected to a considerable extent by the moisture content of the Mowiol film, since water acts as an external plasticizer. As the water vapour content of the air increases, the value for elongation at break rises, while the tear strength decreases. As Mowiol films absorb moisture to different extents, depending on the water vapour partial pressure, precise conditioning must be ensured in any determination of tear strength and elongation at break. The mechanical properties of some selected Mowiol grades are given in Tables 1 and 2, the films having been prepared as follows: films with an approximate thickness of 300 m were cast from aqueous solution. After conditioning for some 3 4 weeks at 23 C and 50% relative humidity, strips 15 mm wide were punched out for testing to DIN 53 455 and stretched to the point of rupture at a rate of 200 mm / min with a free length of 50 mm between the clamps.
E3
The Mowiol Film
Partially hydrolysed Mowiol grades The test produced the load / elongation graph shown in Figure 3:
Fully hydrolysed Mowiol grades The characteristics of load / elongation graph shown in Figure 3 is again found with fully hydrolysed Mowiol grades (Table 2). The difference Fmax FR tends to be higher in fully hydrolysed grades than in the corresponding partially hydrolysed ones. This can be taken as a sign that the orientation tendency of the chains, which are largely free of acetyl groups, is more pronounced.
Tractive force F s = F max
Table 2
Fully hydrolysed Mowiol grades 4-98 53 36 130 10-98 53 34 120 20-98 47 36 130 56-98 52 36 180 28-99 50 36 120
FR
Mowiol Fmax [N/mm2] FR [N/mm2] R [%]
Variation in length L R
Figure 3 Load / elongation graph for Mowiol films (schematic representation) After tension begins the force passes through a maximum (Fmax = tractive force at yield stress) and then declines again. After a further short rise in tractive force the film tears (FR = tear strength and LR = variation in length at tear strength). The first maximum passed through indicates a certain close-order orientation of the polyvinyl alcohol molecule chains over the polar OH groups. Fmax gives the maximum tractive force of a bond when elongation occurs as a sudden, jerking motion. In practice, therefore, this value is more important than FR. Table 1 shows the values found in the test for Fmax, FR and R . Table 1 Mowiol Partially hydrolysed Mowiol grades 4-88 8-88 36 31 130 18-88 26-88 40-88 30-92 48 36 210 49 38 235 50 38 220 60 39 190
Unlike the partially hydrolysed Mowiol grades, the fully hydrolysed grades display virtually no differentiation of values with respect to the degree of polymerization when determined under the given test conditions. All the fully hydrolysed Mowiol grades produce relatively rigid films, comparable with those of the partially hydrolysed series of low molecular weight (see values for R). Rupture tests on plasticized Mowiol films Plasticizing of the Mowiol films changes the nature of the load / elongation graph considerably. As shown by the example of Mowiol 2899, even if only 3% glycerine is added to the polymer the curve (Figure 4) no longer passes through a maximum but rises until the load at rupture is reached. Table 3 shows the change in tear strength and elongation as exemplified by Mowiol 2899 after glycerine is added. Table 3 Mowiol 2899 0 50 110 3 49 330 5 46 345 10 39 530 20 37 680 30 26 770
Glycerine % FR [N/mm2] R [%]
Fmax [N/mm2] 40 FR [N/mm2] 29 100 R [%]
Fmax = tractive force at yield stress (FS) FR = tear strength (DIN 53 455) = elongation at break (DIN 53 455) R When a change is made from low- to high-molecular Mowiol, the tractive force and tear strength increase.
When, for instance, 30% glycerine is added to Mowiol 2899, the elongation at break increases by a factor of 7, while the tear strength falls only by half. This illustrates the good intrinsic strength and toughness of fully hydrolysed Mowiol films even after plasticizing. Note: All the measured values given in Section E 3 were obtained in each case on a single batch of Mowiol.
E4
The Mowiol Film
Tractive force
E 5 Solvent Resistance of Mowiol Films

E 5.1 Water-miscible Solvents
FR
As described in Section C 4, apart from water there are only a few solvents for Mowiol, eg dimethyl sulphoxide, formamide, dimethyl formamide, diethylene triamine and phosphoric acid trisdimethylamide. Mono- and multivalent alcohols such as methanol, ethanol, glycerine, ethylene glycol, di- and triethylene glycol may cause certain Mowiol grades to swell, but not go into solution. Mowiol is resistant to all other solvents even acetaldehyde and acetone if they are present in anhydrous form. As the water content of these solvents rises, their swelling and dissolving capacity for Mowiol increases.
L Variation in length LR
Figure 4 Load / elongation graph of plasticized Mowiol film (schematic representation)
E 5.2
Water-immiscible Solvents
E 4 Gas Permeability
A plasticized, unsupported Mowiol film or a Mowiol coating, eg on paper, is virtually impermeable to gases such as oxygen, nitrogen and carbon dioxide. Mention should also be made of the outstanding resistance of Mowiol coatings or films to solvent vapours and many aromatic substances (see also Section G 1.6). The permeability to oxygen according to DIN 53 380 of a blowextruded Mowiol 1888 film plasticized with trimethylol propane is approximately 1.3 cm3 m2 d1 bar1. This standard, corresponding also to ASTM-D 1434-58, is for a gas moisture content of 0%. As virtually all the properties of a polyvinyl alcohol film depend on the humidity of the air in which storage or the measurement took place, the oxygen permeability rises for Mowiol films, especially in the range where the relative humidity exceeds 50%. Mowiol films have unlimited permeability to water vapour (air humidity) but are not hygroscopic.
Mowiols's resistance to any liquids immiscible with water can be explainded by its chemical structure. The hydrophilic nature of Mowiol gives it outstanding resistance and impermeability to solvents, especially liquid hydrocarbons such as petrol and oil; thus mouldings (films, hoses, seals) made from Mowiol can meet stringent demands in respect of solvent resistance (see Section G 1.6).
E 6 Electrophysical Properties of Mowiol Films

As the polymer has a non-ionic structure, traces of moisture and salts (eg sodium acetate) cause major changes in the electrical behaviour. Measurements to VDE 0303/3 III of the electrostatic surface charge or surface resistance on unsupported Mowiol films with no surface treatment produced values of some 4 107 . The electrical surface resistance of Mowiol films is thus well below the upper limit of 108 that the German Association for the Avoidance of Fire Hazards recommends for the packaging of goods at risk from dust explosion.
Literature A Harrus, W Zimmermann, Plastverarbeiter 32, Nr. 8, 973 (1981)
Literature A Harrus, W Zimmermann, Plastverarbeiter 32, Nr. 8, 973 (1981)
E5
The physiological properties of a substance are important to its processing and to certain uses. In plant physiology, for example, epidermis structures are of special significance. They can be observed by preparing a replica with the aid of Mowiol. Because this polymer is phytotoxically inert, these studies can be carried out on the living plant.
The photograph shows a plant leaf with the polymer film partially stripped off. The structure of the leaf surface is clearly discernible.
Physiological Properties of Mowiol Page
Toxicology / Assessment with Respect to Foodstuffs Legislation Other Information / Safety at Work
F1 F1
F 1 Toxicology Assessment with Respect to Foodstuffs Legislation Other Information Safety at Work
Toxicology Mowiol is toxicologically safe. When tested in animal experiments for toxicological properties and tolerability on the skin and mucous membrane, products in the Mowiol range produced no adverse effects. Mowiol is virtually physiologically inert in terms of acute toxicity (LD50 on rats after oral application). In the 90-day feeding test on rats with selected Mowiol grades there was no deterioration in the animals in terms of behaviour, bodyweight development or food uptake, even with the highest quantity applied (5% in the feed). Moreover, no adverse effects or changes were observed in haematological, clinicochemical and urine tests or in the macroscopic appraisal and histological examination of the internal organs. Mowiol is not a skin irritant according to the FDA (US Food and Drug Administration) patch test. Mowiol is not a mucous membrane irritant according to the FDA irritation test.
FDA examples are 175.105 Adhesives, 175.300 Resinous and polymeric coatings, 176.170 / 176.180 Components of paper and paperboard in contact with aqueous and fatty foods/ with dry food, 177.1670 Polyvinyl alcohol film. Because of their low viscosity, Mowiol grades 383, 488, 396, 398 and 498 can be used for these purposes only to a limited extent, if at all.
Other information Polyvinyl alcohol is described in the DAC (Deutscher Arzneimittel-Codex / German pharmacopoeia) 1986 / 3, PVAL 88 and in the Lexikon der Hilfsstoffe (Compendium of auxiliaries). The polymer group is also listed in the USP (US Pharmacopoeia) 23 Directive. Further information on the use of PVAL in the pharmaceutical sector can be found in the 1983 Code of ophtalmological drugs and medicines [Ophthalneika]. A precondition for the use of polyvinyl alcohol / Mowiol in pharmaceuticals is that it undergoes the usual additional testing for pharmaceutical preparations. Mowiol is permitted in the form of aqueous solutions for the uses described in the German Tobacco Order of 20.12.1977 / Supplement November 1982 as adhesives, bonding agents and thickeners.
Safety at work Repeated dermal application shows Mowiol to have no toxic effect resulting from absorption by the skin. Assessment with respect to foodstuffs legislation Mowiol is a technical-grade product and therefore not recommended for use in foodstuffs. Under various recommendations of the German Federal Health Office / Bundesinstitut fr gesundheitlichen Verbraucherschutz und Veterinrmedizin (BgVV), polyvinyl alcohol / Mowiol can be used for the manufacture of consumer goods as defined by 5 of Germany's Foodstuffs and Consumer Goods Act, and in accordance with Title 21, food and drugs (FDA), of the US Code of Federal Regulations. Examples are the BgVV Recommendations II Unplasticized PVC, XIV Polymer emulsions and XXXVI Paper, cardboard and paperboard for contact with foodstuffs, subject to observance of the restrictions they contain on quantities and viscosity. Polyvinyl alcohol / Mowiol is also listed in Directive 90 / 128 / EEC, Annex II, Section B. Measures should be taken to prevent electrostatic charges and dust explosions (see also Section E 6). Soiling and splashes on the skin should be cleaned off with water. Because of its method of production, polyvinyl alcohol / Mowiol contains small quantities of methanol. Most can be removed by following the prescribed dissolving method and stirring the hot solution over a protracted period possibly in conjunction with an air extraction system (check by GC analysis). During bulk production of Mowiol solution, adequate ventilation of the working area must be ensured. General recommendations relating to the handling of Mowiol are contained in the Technical Data Sheet on Safety at work and environmental protection. Material Safety Data Sheets [MSDS] and Recommendations for Labelling will be provided on request. The handling of Mowiol entails no health risk. Inhalation of any dust occuring during processing should be avoided for general health reasons (dust masks should be worn).
F1
Uses of Mowiol
G
Differences in polymer structure and interesting, diversified properties such as water solubility, film formation and binding power open up a wide variety of uses for the polyvinyl alcohol Mowiol. For example, in the fields of paper, polymerization, adhesives, textiles, plastic film and ceramics. Some of these uses are shown in the collage.
Uses of Mowiol Page
1 1.1 1.1.1 1.1.2 1.1.3 1.2 1.2.1 1.2.2 1.3 1.3.1 1.3.2 1.4 1.4.1 1.4.2 1.4.3 1.4.4 1.5 1.5.1 1.5.2 1.5.3 1.6 1.6.1 1.6.2 1.6.3 1.7 1.8 1.9 1.10 1.11 1.12 1.12.1 1.12.2 1.13 1.13.1 1.13.2 1.13.3
Uses based primarily on Physical Properties of Mowiol Mowiol as Emulsifier / Protective Colloid Mowiol in polymer emulsions Properties of polymer emulsions containing Mowiol Production of polymer emulsions by emulsion polymerization Mowiol as a Raw Material in the Textile Industry Raw material for sizing agents Raw material for finishing and as a temporary adhesive for screen printing Mowiol as Raw Material for Adhesives Water-activated adhesives and wet bonding Modification of emulsion adhesives Mowiol in the Paper Industry Coated papers Surface sizing Special papers Heat-sealable paper coatings Mowiol as Temporary Binder Ceramic compounds Ferrite cores Pelletizing Thermoplastic Processing of Mowiol Plasticizing Film extrusion Injection moulding Mowiol in Protective and Strippable Coatings Solvent-resistant Dip-coated Mowiol Articles Mowiol as Release Agent for Casting and Laminating Resins Production of Detergents and Cleaning Agents with Mowiol Mowiol in Plant Protection Agents Mowiol in the Metal Industry Secondary brightener in electroplating Quenching baths for steel Mowiol in the Paint Industry Roller-applied filling compounds Wood primers Distempers and watercolours
G1 G1 G1 G2 G3 G3+G4 G3+G4 G5 G5 G5 G6 G6 G6 G6 G7 G7 G8 G8 G8 G9 G9 G9 G 10 G 12 G 12 G 12 G 12 G 14 G 15 G 15 G 15 G 16 G 16 G 16 G 17 G 17
Uses of Mowiol Page 1.13.4 1.13.5 1.14 1.15 1.16 1.17 1.18 1.19 2 2.1 2.2 2.3 2.4 2.4.1 2.4.2 2.5 2.6 Emulsion paints Artist's pastes / finger paints Mowiol in the Building Industry Mowiol in Cosmetics Fluorescence Analysis Microencapsulation Replicas (Plant Physiology) Preservation and Restoration Applications based mainly on the Reactivity of Mowiol Acetalyzation / Polyvinyl Butyral / Mowital B
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Spinning and Hardening of Fibres Mowiol Sponges Consolidation of Nonwovens Glass fibre nonwovens Textile nonwovens Photosensitive Coatings Offset Printing Plate Coatings / Printing-Screen Lacquers / Colour Television Screens Printing Inks for Decor Papers
Uses of Mowiol
G 1 Uses based primarily on Physical Properties of Mowiol

G 1.1 Mowiol as Emulsifier / Protective Colloid
Much of the Mowiol produced is used as a protective colloid in the manufacture of polymer emulsions. This special application was first discovered in the plastics laboratory of Hoechst AG [1]. As a method of stabilizing polymer emulsions it has given sterling service over the years. Emulsions stabilized with Mowiol contain polyvinyl acetate (PVAC) as the predominant, and often the only polymer. For copolymer emulsions, the products generally used alongside vinyl acetate as comonomers are esters of acrylic acid, esters of maleic acid, vinyl esters of higher fatty acids or ethylene [2]. To obtain certain properties in the emulsions, eg to achieve freeze / thaw stability, pigment compatibility and bond strength in glued bonds, small quantities of unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid or their semiesters) can be added during polymerization [3]. Not only can Mowiol be introduced as a protective colloid at the time when the emulsion is being produced, but it can also be added to polymer emulsions after manufacture and thus produce marked changes in their properties (see Section 1.3.2). Finally, another use of Mowiol is of considerable importance: that of stabilizing agent in bead or suspension polymerization of styrene and vinyl chloride.
Literature [1] German State Patent 727 955 [2] German State Patent 1 127 085 [3] German State Patent 803 956
The principal grades of Mowiol used are the partially hydrolysed ones. These polyvinyl alcohols are adsorbed particularly well on the surface of the latex particles. This gives rise to a protective coating on the latex particles which protects the emulsion against coagulation during polymerization and finally protects the finished emulsion during mechanical stress as well as during freezing and rethawing. Because of the greater interfacial activity of partially hydrolysed Mowiol (see Section D 4) it is possible in this way to produce finer emulsions of high viscosity than fully hydrolysed Mowiol allows. Partially hydrolysed Mowiol also improves the compatibility of an emulsion with pigments and inorganic salts. The fully hydrolysed Mowiol grades are only rarely used alone as protective colloids in the manufacture of polyvinyl ester emulsions. To obtain specific properties they are combined with partially hydrolysed Mowiol and sometimes emulsifiers. Fully hydrolysed Mowiol used as a protective colloid improves the waterresistance, tear strength and notch impact toughness and reduces the blocking tendency of emulsion films. The non-foaming tendency is an advantage in this case (see Section D 4.1). In polyvinyl acetate emulsions, Mowiol has a particularly good stabilizing action compared with other protective colloids. No emulsifier or other dispersing aids need be added [1, 2]. Where ionic or non-ionic emulsifiers are used together with Mowiol in the production of polyvinyl ester emulsions, this is done to obtain special effects, eg a given latex particle size and particle size distribution [3]. Where only Mowiol is used as a stabilizer in the production of polyvinyl ester (particularly polyvinyl acetate) emulsions, relatively coarse-grained emulsions are obtained with an average particle size of 13 m. Such emulsions are highly suitable as raw materials for wood glues and paper adhesives. The simultaneous use of emulsifiers makes for finer emulsions (average particle size 0.2 1m) of the type needed as binders in paints. By adjusting the ratio of Mowiol to emulsifier it is possible to obtain the most favourable particle size for a particular purpose. In addition to the degree of hydrolysis and quantity of Mowiol, its viscosity also plays an important part in determining the average particle size of an emulsion. The higher the viscosity for a particular quantity of protective colloid, the coarser will be the particles of the emulsion. The relationship between average particle size and viscosity of the Mowiol solution used in the manufacture of a polymer emulsion is shown in Figure 1.
G 1.1.1 Mowiol in polymer emulsions In the production of polymer emulsions, up to 10% by weight of Mowiol relative to emulsion is used. The function of Mowiol in this case is to keep the monomers being polymerized in an ultrafine state of dispersion during production of the emulsion and to stabilize the finished emulsion against coagulation. This additive also contributes substantially to the specific properties of the emulsion.
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Uses of Mowiol
m Particle size 0,5
the tendency to form aggregates. This is accompanied by improvements in the emulsions' shear, storage and dilution stability. If monomers other than vinyl acetate are used in polymerization, stabilization with Mowiol alone will often not be sufficient. In the production of copolymer emulsions, ionic and / or non-ionic emulsifiers are therefore used as well.
Literature
0,4
[1] German State Patent [2] German State Patent US Patent German State Patent
727 955 745 683 2 398 344 887 411
[3] US Patent US Patent US Patent US Patent German State Patent
2 508 341 2 398 344 2 388 600 2 694 052 901 936
G 1.1.2 Properties of polymer emulsions containing Mowiol
0,3
Polymer emulsions containing Mowiol are employed in a wide variety of uses, such as the paints, building, and glue and adhesives sectors. In the paint sector it is mainly homopolymer and copolymer emulsions based on vinyl acetate which are used, these being produced with combinations of Mowiol as protective colloid and emulsifiers. The emulsions have good pigment-binding power and emulsion paints made from them are easy to use. High-Mowiol-content emulsions produced without emulsifiers or in the presence of only small quantities of emulsifier are used with great success in the glue and adhesives sector. The practical requirements, which are important for wood glues, namely long open time, high setting rate and good bond strength, can be satisfied with glue emulsions made with Mowiol. Polyvinyl acetate emulsions produced with Mowiol are also well-known as quick-setting adhesives for paper. The film-forming temperature of polymer emulsions can be reduced by adding external plasticizers. These are used in quantities of up to 50% by weight, relative to the polymer. As well as lowering the film-forming temperature, the addition of plasticizer increases the flexibility and water-resistance of the emulsion film. The polyvinyl acetate emulsions made with Mowiol as protective colloid have good compatibility with plasticizers such as dibutyl phthalate, di-iso-butylphthalate or tricresyl phosphate.
0,2 0 10 20
Viscosity m Pa . s 30 40 40-88 50
4-88 8-88
18-88 26-88
Mowiol grade
Figure 1 Average particle size of an emulsion as a function of Mowiol grade used It is often necessary to obtain a given latex viscosity. Here again as during adjustment of the average particle size, the quantity and viscosity of the Mowiol are important. Thus Mowiol 488 and 498 produce low-viscosity emulsions suitable under production conditions for processing on high-speed machines. On the other hand, if Mowiol 888, 1098, 4088 or 5698 is used, the emulsions will be highly viscous or paste-like. In formulations with a high emulsifier content, higher quantities of Mowiol result in larger latex particles; but in emulsifier-free polymerization they cause a reduction both in particle size and in
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Uses of Mowiol
Polyvinyl acetate copolymer emulsions made with Mowiol have proved their value in the film-bonding sector, in which the bonds need to have high thermal stability. High-Mowiol-content emulsions are of great interest in the glue and adhesives sector. Among the reasons is their considerable adhesive strength when wet. Significantly, as the quantity of Mowiol increases, the emulsions become more hydrophilic and the films made from them are easier to re-emulsify. Mowiol can also be added to aqueous polymer emulsions after manufacture. It then produces substantial changes in properties, such as Increased viscosity Improved rheological properties Improved resistance to cold Improved stability to inorganic salts or pigments Increased open time in use Improved adhesion, especially on materials containing cellulose. Figure 2 shows various possibilities for adjusting the latex viscosity, the polyvinyl acetate emulsion being the same in each case. In this instance, first an aqueous solution of Mowiol 1888 (3), secondly an aqueous solution of Mowiol 488 (2), and thirdly pure water (1) were added to an approx 60% emulsion.
m Pa . s 15 000
Viscosity (Contraves-Rheometer STV)

3 Basic emulsion mixed with Mowiol 18 88 solution, additional Mowiol content 2 %, relative to solids content 2 Basic emulsion mixed with Mowiol 4 88 solution, additional Mowiol content 2%, relative to solids content 1 Basic emulsion mixed with pure water, Mowiol content 9%, relative to solids content
1 0 000
5 000
60
55
50 % Solids content
G 1.1.3 Production of polymer emulsions by emulsion polymerization Polymer emulsions can be produced by continuous or discontinuous polymerization processes. The discontinuous polymerization processes include, for example, the batch process, the gradual monomer addition process and the gradual emulsion addition process. In the batch process the whole of the monomer is introduced with the solution at the beginning and polymerization is started by heating or by adding initiator. In the gradual monomer addition process the bulk of the monomer is added to the reaction vessel over a period of several hours after polymerization has started. One special form of monomer addition process is the gradual emulsion addition process, in which the monomer is added to the reactor after emulsification in water. The process affects important parameters of the emulsion, for example the latex viscosity and the size of the latex particles. In
Figure 2 Adjusting the latex viscosity of a polyvinyl acetate emulsion with a standard solids content of approx 60% by adding Mowiol solution or water
the batch process the emulsions obtained are generally coarser than in the gradual monomer addition process. Laboratory tests should be used to determine the most suitable polymerization process for achieving specific application properties in the emulsions, as well as the appropriate quantity of emulsifiers and protective colloids. Apparatus suitable for these tests is shown in Figure 3.
G 1.2
Mowiol as a Raw Material in the Textile Industry
G 1.2.1 Raw material for sizing agents In the textile sector Mowiol is used mainly for sizing all kinds of warp material [1, 2].
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Uses of Mowiol
Antistatic surface Low viscosity in the size solution to facilitate penetration into the fibre core and allow high programmed efficiency levels on modern cylinder sizing machines Ease of removal from fibres by washing out
R
5
T
3 1 5
6 7
Slight differences occur between the partially and fully hydrolysed Mowiol grades in the way that they meet the demands placed on them as raw materials for sizing agents. While the rate of dissolution and thus the ease with which the sizes can be washed out of the fabric are relatively high for partially hydrolysed Mowiol grades, these products have a more or less pronounced tendency to foam. Foaming occurs particularly if the production vessels are fitted with high-speed intensive mixers but also if the solution is agitated too vigorously in the sizing machines or high production rates are employed. There is reluctance to use defoamers in sizing solutions because they usually have a detrimental effect on the adhesion of the size film. In cases where foaming is inevitable, it can be helpful to replace the partially hydrolysed Mowiol grade with an equiviscous fully hydrolysed grade up to a proportion of 1 : 1. This scarcely changes the optimum sizing effect. The concentration of the sizing solutions is some 10 40%; so the partial incompatibility of partially and fully hydrolysed Mowiol grades has to be borne in mind (see Section D 7.2.7). It takes longer, and higher temperatures are required (approx 85 90C), to wash out a size film made with fully hydrolysed Mowiol, especially where the application is heavy or the weave is dense.
1 2 3 4
2-litre four-necked flask 5 Inside/outside Reflux condenser thermometer Stirrer 6 Immersion heater Dropping funnels 7 Water bath
Figure 3 Diagram of test apparatus for emulsion polymerization
Advantages of Mowiol as raw material for sizing agents: The purpose of sizing is to strengthen the warp threads as carriers for weave constructions so that in the weaving process the fibres are undamaged by mechanical stress and optimum weaving efficiency is achieved as well. Sizing is also used to avoid thread breakage as a result of insufficiently protected warp threads. A sizing agent should be selected on the basis of the following features, having regard to the fibre material to be sized: Good penetration Good adhesion and cohesion (adhesive strength) Good film-forming capacity, yielding films whose elasticity and elongation coupled with simultaneous freedom from blocking are also important Convenient form of supply as granules comprising virtually 100% active substance Possibility of selection from various graded viscosities Stability in the form supplied and made-up solution at temperatures including the whole range normally used for the sizing process High adhesive and cohesive strength of the Mowiol film compared with natural products, thus allowing substantial reductions in the quantities of size used and greatly reducing abrasion (with accompanying dust) on the sizing machines and looms High elasticity, tear strength, flexibility and surface smoothness of warp material sized with Mowiol
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Uses of Mowiol
Good separability of yarns sized with Mowiol, which prevents detachment of individual filaments during yarn separation Continuing low viscosity of sizing solutions even in high concentrations, thus allowing high production rates in the sizing process. Mowiol, prepared with other substances where necessary, is thus an excellent raw material for sizing the following types of fibre: Staple yarns of natural, semi-synthetic and fully synthetic fibres, alone or intermixed Filament yarns of viscose, secondary acetate, triacetate and cuprammonium rayon, and polyacrylic nitrile filaments. PVAL textile sizes can be re-used. Various methods for recycling these sizes have been developed, ultrafiltration being of particular interest (see Section H 2) [3, 4, 5, 6, 7, 8, 9, 10].
G 1.3.1 Water-activated adhesives and wet bonding Remoistenable adhesives are used mainly in the paper-processing industry, particularly for gumming the reverse face of papers (postage-stamps, labels) and the flaps on envelopes and Jiffy -type bags. The products used for the manufacture of water-activated adhesives are the low- to medium-viscosity Mowiol grades, especially those which are partially hydrolysed such as Mowiol 383 and 488, etc, to Mowiol 2388. In selecting the Mowiol grade it has to be borne in mind that the low-viscosity products have a longer open time after wetting (activation) than those of high viscosity. The higher-viscosity Mowiol grades, on the other hand, produce greater strength in the bond. Depending on the viscosity requirement for the application machinery and also on the Mowiol grade chosen, the solutions prepared for application have a solids content of up to 30%, preferably together with added preservative and defoamer. Drying of the applied layer of adhesive can be accelerated by the addition of alcohols or Mowilith emulsions such as Mowilith DH 257 approx 50% or Mowilith DM 2 approx 55%. The drying temperature must be as low as possible and should not exceed approx 130C; otherwise the activation of the adhesive coating will be impaired. An applied quantity of approx 10g of Mowiol 488 per m2 will produce coatings which are readily remoistenable with water and offer the following advantages: Good flatness in storage, even with changes in humidity
Literature [1] J Trauter, M Laupichler, Melliand Textilber. 56, 706, 800 (1975) [2] J Trauter, N A Ibrahim, Melliand Textilber 3, 199 (1990) K Ramaszder, Melliand Textilber. 8, 592 (1991) [3] O Deschler, Melliand Textilber. 12, 1003 (1979) [4] O Deschler, Melliand Textilber. 1, 42 (1980) [5] J Trauter, W Armbruster, Melliand Textilber. 7, 571 (1980) [6] J Trauter, Textil Prax. Int. 3, 239; 5, 470 (1983) [7] J Trauter, Textil Prax. Int. 6, 599 (1983) [8] O Deschler, Melliand Textilber. 10, 716 (1983) [9] J Trauter, Melliand Textilber. 1, 17 (1990) [10] G Schmid, Melliand Textilber. 7, 557 (1991) [11] J Trauter, R Vialon, Th Stegmaier, Melliand Textilber. 8, 595 (1991)
G 1.2.2 Raw material for finishing and as a temporary adhesive for screen printing Mowiol is used as a water-soluble adhesive for continuous fabrics on screen-printing tables. It is also suitable as a raw material for special finishing processes, eg the stiffening of collar linings in shirts.
Colourlessness and flexibility Minimal blocking tendency, even at high air humidity Rapid setting after reactivation. High-viscosity and fully hydrolysed Mowiol grades such as Mowiol 2098, 2899 and 5698 are used when the requirement is for cold- water-resistant bonds. Such applications include the manufacture of special paper laminates, cardboard and both spiral-wound and parallel-wound tubes, besides packaging closures, for which uses the high-viscosity and fully hydrolysed Mowiol grades usually produce greater wet-tack as well. Aqueous adhesives based on Mowiol can also be extended with fillers such as china clay. For spiral-wound tubes or the flat bonding of paper and cardboard, these extended adhesives still yield firm bonds even in proportions of some 2 parts by weight of filler to 1 part by weight Mowiol. The action of boric acid is described in Section D 6.2 on page D 20.
G 1.3
Mowiol as Raw Material for Adhesives
Like starch, starch degradation products (dextrins) and casein, Mowiol can be used as a raw material for the production of aqueous adhesives solutions. Mowiol has the advantage over dextrin and casein of being chemically uniform in structure and having high adhesive strength with minimal raw material input.
Literature A Harrus, Hoechst AG/Resin News 25, 11 (1988)
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Uses of Mowiol
G 1.3.2 Modification of emulsion adhesives Mowiol can be added in the form of its aqueous solution to predominantly polyvinyl alcohol-stabilized emulsions, thereby producing the following effects: Longer open time Faster setting Modified rheology. The open time is very important, eg in the craft trades and the machine-bonding of wood or paper. The addition of Mowiol solutions to the adhesive emulsions also helps ensure the perfect processing of adhesive in gluing equipment which is not totally enclosed, such as pick-up / applicator wheels, and rollers in partially or fully open glue tanks, and often prevents skinning. In a number of emulsions such as Mowilith D approx 50% the addition of Mowiol solution sometimes greatly increases the setting rate. Quantities of up to 10% of an approx 15% solution have proved effective. The choice of Mowiol grade depends in the first instance on the desired viscosity of the adhesive. Mowiol 488 is used for lowviscosity adhesives and Mowiol 1888 to 4088 for higher viscosities. Generally it is preferable to use the partially hydrolysed Mowiol grades because of their better dissolving properties (see also Section G 1.1.2). Mowiol can be used in combination with cellulose or emulsifier-stabilized Polymer emulsions. Particular attention must be paid to the shelf life. It is recommended that the Mowiol grade and quantity added be determined by preliminary trials.
Mowiol has to be applied by coating the surface only. If used in the paper mass, Mowiol would not adhere to the fibres, but accumulate in the binding compound.
G 1.4.1 Coated Papers Apart from the primary binder being used. Mowiol is preferably used in coating colours as a water soluble synthetic cobinder. Mowiol is particularly suitable for this area of application because it possesses the following properties: Outstanding carrier properties for optical brighteners; more than any other cobinder, Mowiol is able to boost the performance of the brightening agents which in turn leads to higher whiteness of paper. Excellent colloid protection properties allowing a smooth running process with compounds of stable viscosity. The low molecular weight Mowiol grades are well suited for ultra high sheer coating colours if their amount is kept below 1.0% related to the pigment. Marked contribution to the pigment binding strength and thereby to the pick resistance of the coating. Mowiol supports wetting and adhesion to every kind of pigment. Good water resistance of the coating when fully hydrolysed Mowiol grades are used. For coating purposes Mowiol 398, 498, 698 and also Mowiol 588 are preferably used. The required amount is 0.5 1.5% referred to the pigment. Coatings are mostly applied by using blade coaters. When manufacturing a coating colour, the addition of polyvinyl alcohol solution to Clay slurries may result in a spontaneous viscosity increase (pigment shock), which occurs at around 0.2 g PVAL/100 g Kaolin. A pigment shock can be avoided by putting the Mowiol solution into the vessel first, then adding the Clay slurry while stirring (4).
Literature A. Homanner, Hoechst AG/Resin News 21, 30 (1984)
G 1.4
Mowiol in the Paper Industry

G 1.4.2 Surface sizing The predominant features of Mowiol are its solubility in water, its excellent film forming properties and its good adhesion to fibres and fillers. Mowiol is therefore used as an approved binder for the surface treatment of paper and cardboard. It enhance the structural and surface strength of these materials. Furthermore Mowiol is apt to form barrier coats against hydrophobic substances. The effectiveness of sizing depends on the properties of the base paper, the choice of Mowiol grade (5) and the conditions of application. The following aspects in particular are to be positively emphasized.
Among the many products used in paper making Mowiol offers the following remarkable properties which particularly take effect in the paper finishing. There are as follows: Outstanding carrier properties for optical brighteners (1) High binding power for pigments and fibres (2) Excellent barrier properties (3) Good strength values
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Uses of Mowiol
Mechanical strength values such as tensile strength and elongation, bursting pressure and double fold endurance. Dimensional stability and flat surface level. Surface strength (e.g. in z-direction) Barrier effect against hydrophobic compounds. Papers treated with fully hydrolysed Mowiol grades will almost not change in terms of water absorption (Cobb-value). Mowiol is able to tie down the fibres and to help adsorb filler particles to the fibre. Thus picking and dusting during printing is largely reduced. The barrier properties of papers surface sized with Mowiol are utilized in the production of many special paper grades. G 1.4.3 Special Papers The insolubility of Mowiol in most organic solvents, oils, fats and waxes, combined with its good filmforming properties allows the manufacture of special papers with specific barrier features. Since the Mowiol grades encompass different molecular weights and degrees of hydrolysis, the properties of special papers can be tailored according to their requirements. The fact that Mowiol can be readily combined with other natural or synthetic binders or special chemicals opens up a wide range of uses in the paper field (6). Mowiol as a nonionic product complies with anionic additives as well as it does with cationic auxiliaries. Owing to its barrier effect to silicon resins, Mowiol is particularly suitable for the manufacture of silicon base papers which are widely used as release papers for labels glued with pressure sensitive adhesives. The high internal strength (cohesion) and the heat resistance of Mowiol film, combined with its release properties can be employed to produce so-called film casting papers for flexible PVC and PU foils. Mowiol displays outstanding barrier properties to oil and fats which may be further enhanced by adding oil and fat repellent compounds such as fluoro chemicals. Thereby grease-proof papers if desired, also in compliance with the food regulations can be manufactured. Mowiol is also useful for the production of aroma-proof and steam-proof coatings. For the latter case certain latices must be employed, too (7). The outstanding solvent holdout by using Mowiol can be utilized to produce autocopying (NCR-) papers and electrophotographic papers. Mowiol films show high thermal stability and excellent resistance to fatty compounds, solvents and plasticizers. This pro-
perty profile represents just the right requisite for the manufacture of thermosensitive papers. These are widely used for products such as bar code labels and fax papers (8). Mowiol plays a particular role in the production of coated and non-pigmentized inkjet papers. Thus Mowiol is employed as a sole binder in pigmented coatings (e.g. using silica gel powder). For surface sizes not containing pigments Mowiol is chosen as the major compound in order to ensure a fast ink set-off and a high brilliance of colours (9). Straight surface treatments of paper with Mowiol leads to improved dimensional stability and to enhanced folding endurance used to produce base papers for bank notes and maps. G 1.4.4 Heat-sealable paper coatings After being plasticized with glycol, polyglycol, glycerine or other of such plasticizers, Mowiol can be used for heat-sealable paper coatings. Grades 488, 888, 498 and 1098 are particularly suitable for this purpose. Plasticizing is carried out typically with 10% glycerine, relative to Mowiol. The sealing temperature and time are predetermined by the grade of Mowiol, amount of plasticizer and the coat weight applied. Thus, for a sealing time of 0.5 seconds the following sealing temperatures have been obtained: Mowiol 488 + 10 % plasticizer (e.g. glycerine): approx. 165 C Mowiol 498 + 10 % plasticizer (e.g. glycerine): approx. 195 C Changing over from a partially to a fully hydrolysed Mowiol grade of the same viscosity, it is possible to raise the sealing temperature noticably.
Literature [1] HG Oesterlin, H Schaefer, Das Papier 32, 10A, V 13 (1978) HG Oesterlin, Das Papier 36, 66 (1982) F Mller, D Loewe, B Hunke, Wbl. f. Papierfabrikation 6, 191 (1991) P Hentzschel, G Martin, R Pelzer, K Winkler, Wbl. f. Papierfabrikation 5, 176 (1998) [2] L Goettsching, K Helyes, Wbl. f. Papierfabrikation 11/12, 359 (1973) R Vesanto, H Schaefer, D Wolf, Paperi ja Puu 5, 1975 [3] B Reinhardt, L Frilund, Wbl. f. Papierfabrikation 11/12, 486 (1989) B Reinhardt, Wbl. f. Papierfabrikation 6, 198 (1992) [4] Polyvinyl Alcohol (CA Finch), J Wiley & Sons 1973 W Schempp, W Friesen, JSchurz, Tappi 58, 116 (1975) H G Oesterlin, Das Papier 32, 150 (1978) M Mkinen, D Eklund, 1996 Tappi Coating Conference, 61-78 [5] H G Oesterlin, Allgemeine Papier-Rundschau 44, 1242 (1982) [6] D Wolf, Hoechst AG, Resins News 17, 34 (1981) [7] N L Thomas, Progress in Organic Coatings, 19, 101 (1991) Patria Papier & Zellstoff, EP 0487497A1 v. 18.11.91 [8] Heat-sensitive recording materials, Ricoh K.K., EP 0238709B1 v. 10.09.86 [9] P Hentzschel, R Pelzer, Wbl. f. Papierfabriaktion 18, 795 (1996)
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Uses of Mowiol
G 1.5
Mowiol as a Temporary Binder
Low binder requirement Low ash content (electroceramics) Little waste through breaking (re-usable) Smooth burn-out profile Low shrinkage during firing No clogging of screens, filters and moulds.
G 1.5.1 Ceramic compounds Mowiol is outstandingly suitable as a temporary binder and plasticizer for ceramic compounds. It breaks down almost entirely into water and carbon dioxide when a ceramic moulding is fired. The possible applications depend essentially on the nature of the ceramic compound and the moulding process. The quantities used vary considerably, depending on the technology applied, in the range 0.1 5%, relative to the dry mix. Mowiol is particularly effective as a temporary binder in special ceramics (technical ceramics). In this sector mouldings of high green strength are made by cold compression of ceramic powder produced beforehand by spray drying [1]. In special ceramics it is important to have both high green strength in the moulding and the lowest possible viscosity in the aqueous ceramic slip, the necessary shear-dependent viscosity being achieved by the addition of Mowiol. If the slip needs to be further liquefied for particular uses, this can be done by adding Mowilith Ct 5 A approx 50% in solution, sodium hexametaphosphate and / or other dispersants. In the case of low-viscosity compounds it should be noted that foaming may occur during vigorous mixing. To prevent this, additions of 0.02 0.3% defoamer, relative to Mowiol / solid, are recommended (see Section D 4.1). Mowiol 383, 888, 1888 and especially 488, though also fully hydrolysed grades such as Mowiol 1098, have proved useful in the ceramics sector. These products are applied either alone or with an addition of up to 10% plasticizer (relative to Mowiol) such as glycerine, glycol, trimethylol propane, neopentyl glycol or polyglycol (up to a molar mass of 400). During development work on suitable formulations, consideration may be given to additions of paraffin emulsions or solutions of polyglycols with higher molar masses, the choice depending on the process technology. The combination of Mowiol with cellulose ethers (Tylose) in ceramic slips gives improved processability, eg in the plasticizing of extrusion compounds. Advantages of using Mowiol as a temporary binder in the ceramics sector: Low viscosity of the aqueous slip before drying and hence less water to evaporate (energy saving)
Literature [1] H B Ries, Keramische Zeitschrift 23, No 9, 516 (1971) a. 10, 591 (1971)
G 1.5.2 Ferrite cores The production of ferrite cores as bodies for high-frequency coils uses a procedure familiar from the manufacture of special ceramic components. Here again an aqueous slip, after being mixed with Mowiol solution, is converted by spray drying into a powdery dry compound, cold compressed in a mould, then machined and finally sintered [1]. In ferrite core manufacture, fully hydrolysed Mowiol grades are preferred because of their lower tendency to foam. The core material is mainly ferric oxide Fe 2O3 with a maximum alkali impurity of 0.03%. Only in this way can high quality ferrite material be obtained. Similar purity requirements relating to electrolyte content should be imposed on the temporary binder. Because of the high pigment-binding power, very small quantities of Mowiol (0.1 0.5%, relative to solids component) are sufficient to raise the mechanical strength of the pressed moulding substantially before sintering. For the low-viscosity Mowiol grades concerned it is possible with a maximum of 0.5% sodium oxide to guarantee a very low ash content, so that the sodium content introduced by the temporary binder Mowiol is smaller by some orders of magnitude than that of the oxide base material. As a temporary binder Mowiol burns away almost completely at the high sintering temperature of 1100 1400C. In the production of the slip it is advisable to add Mowilith Ct 5 A approx 50% in solution or ammonium citrate as liquefier of the ferric oxide / Mowiol solution system.
G8
Uses of Mowiol
G 1.5.3 Pelletizing Pelletizing of materials in powder form is used mainly to reduce or eliminate the dust nuisance which inevitably occurs in processing. Pelletizing substances are also easier to store, transport, dissolve and package [1]. In the pelletizing operation the powders are converted into spherical granules with the aid of suitable binders [2]. After pelletizing, the product is free-flowing, easy to handle and almost dust-free. The pellets, which contain between 0.5 and 5% Mowiol as binder, depending on the type of material used, can be made in various sizes. Low molecular, partially hydrolysed grades such as Mowiol 383, 488 and 588 are preferred as binders because they present no problems for the production of sprayable solutions with variable solids content. Furthermore, the active substances bound in the pellets have to be quickly ready for use again after dissolving, eg in water.
Literature [1] H B Ries, Aufbereitungs-Technik 4 (1981) H B Ries, Keramische Zeitschrift 35, No 2, 67 (1983) [2] H B, Ries, Aufbereitungs-Technik 20, No 12, 660 (1979)
Depending on the degree of hydrolysis of the Mowiol grade used and the extrusion conditions, mouldings with graduated watersolubility can be produced. Other properties of mouldings made from Mowiol compared with familiar plastics: Biodegradability of the aqueous solution Resistance to most organic solvents (see Section C 4 and E 5) Good mechanical values Non-toxicity Good barrier action against oxygen, nitrogen, many aromas and perfumes (see Section E 4). With these properties, thermoplastic mouldings in Mowiol are useful for the following applications: Films: portion packaging for toxic substances, oils and fats, plant protection agents, detergents and seeds; hospital laundry bags, hygiene products, films permeable to water vapour for bed undersheets, packaging of medical and cosmetic requisites; release film for GRP production; composites permeable to water vapour but resistant to water Tubes and profiles: solvent-resistant hoses, trims and seals Injection mouldings: casings for fireworks and ammunition, membranes for oil and petrol pumps, plugs for the building sector.
Literature A Harrus, W Zimmermann, Plastverarbeiter 32, 973 (1981)
G 1.6
Thermoplastic Processing of Mowiol
In view of its chemical constitution polyvinyl alcohol could be described as a theramoplastic polymer. Depending on the dwell time, however, polyvinyl alcohol tends to release water from the molecule chain by cleavage at high temperatures of about 150 C or more. This chemical reaction is subject to the following mass action equilibrium: PVAL PVAL + nH2O PVAL' here represents those parts of the polyvinyl alcohol chain which have released n molecules of water by cleavage. Higher temperature and longer dwell times shift the equilibrium to the right, whereas the addition of water and application of pressure under the same conditions shift the equilibrium towards the thermoplastic PVAL. A prerequisite for thermoplastic processing of polyvinyl alcohol is therefore prior plasticizing of the polymer with the familiar plasticizers and water. The fine granule form in which Mowiol is supplied provides ideal conditions for plasticizing the product in a forced circulation mixer. The Mowiol blend can be processed on standard thermoplastic processing machines such as blow extruders, injection moulding machines and compression moulding equipment.
G 1.6.1 Plasticizing In order to process Mowiol on standard plastic processing machinery such as profile extruding machines, blown film extruders or injection moulding machines, the undesirable thermal decomposition of the product at temperatures above 150 C must be prevented by external plasticizing of the granular Mowiol. With its fine granular form and relatively uniform grain size distribution, the Mowiol can be homogeneously platicized in a forced-circulation mixer similarly to the cold dry-blend production of PVC [1, 2, 3]. Suitable platicizers include, in the first instance, water and polyvalent alcohols such as glycerine, trimethylol propane, diand triglycol and neonpenthyl glycol (see Section E 2), the quantity added being 5 50% relative to the mixture. Other additives
G9
Uses of Mowiol
Henschel, Kassel, Germany (Fluid Mixers),
% Screenings 99,9 99 95 90 80 70 60 50 40 30 20 2 10 1 5 4 3 2 1 0,5
Ldige, Paderborn, Germany (Forced Circulation Mixers), T K Fielder Ltd, Eastleigh (Hants.), UK (Turborapid Mixer), and others. The grain size distribution of Mowiol is further standardized by the mixing process (Figure 4, grain characteristic 2). The Mowiol-plasticizer blend is a free-flowing and non-blocking. It can be used without further treatment, eg granulation, as feedstock for standard thermoplastic processing machines. The following partially and fully hydrolysed products are suitable for plasticizing and subsequent thermoplastic processing: Mowiol 15 79, 4 88, 5 88, 8 88, 18 88, 23 88, 26 88, 40 88, 30 92, Mowiol 10 98, 20 98, 28 99, combinations of these grades are often used.
Literature [1] Hoechst AG, EP 000 4587 [2] Hoechst AG, U.S. Pat. 4 369 281 [3] A Harrus, W Zimmermann/Hoechst AG, Resin News 14, 1 (1978)
G 1.6.2 Film extrusion The Mowiol-plasticizer blends produced in accordance with Section G 1.6.1 can be processed in vented extruders with specialpurpose screws to produce tubular film, blown film, flat film and continuous profiles. Blown film extrusion is the preferred use [1].
0,1
0,2 0,3 0,5
3 4 6 Grain mm
Because of the water content of Mowiol blends, however, the extrusion process is fundamentally different from that of polyolefin processing in the following respects: Extruder fed via a metering device Temperature programme from feed hopper to blown film die dropping from some 220 to 150C (depending on Mowiol grade and plasticizer concentration) Feed zone water-cooled if possible
Figure 4 Grain size distribution before (1) and after (2) plasticizing of Mowiol 18 88
such as colorants, lubricants and anti-blocking agents can be included in the plasticizer. Compounding takes place in a forced-circulation mixer as a diffusion-controlled process, ie a process dependent on the mixing time and temperature. The mixing times are 15 30 minutes according to the Mowiol grade at a temperature of up to 110 C. Forced-circulation mixers made by the following companies are among those suitable for producing Mowiol-plasticizers blends: Papenmeier GmbH Mischtechnik, Paderborn, Germany. (Dry Blenders), Drais, Mannheim-Waldhof, Germany (Turbulent Rapid Mixers),
Blow-up ratio at blown film die can be up to 1 : 8. The Mowiol grade (degree of polymerization and hydrolysis), plasticizer concentration, extrusion temperature and dwell time in the extruder barrel determine the cold water solubility of a film. Films that dissolve very rapidly in cold water are produced with partially hydrolysed Mowiol grades, minimum dwell time in the extruder and the lowest possible extrusion temperature. By means of these parameters it is possible to increase systematically the dissolving time or temperature of a Mowiol film in water up to insolubility at 80 C.
G 10
Uses of Mowiol
Table 1
Performance chart for Mowiol films
Packaging
ge nt s
Other uses
es
na
nt
ts uc
nc
dr
cto se Sa ni t
lve
ite
ts
t io
od
uc
un
ta
os
so
ec
bs
ts
pr
l la
od
mp
en
ts,
pr
ne
su
ita
tri
pr
fa
rg
sty
gi e
ic
sp
co
To x
nt
te
ls,
Hy
Ho
Pl a
Du
Rapidly soluble in cold water Slowly soluble in cold water Insoluble in cold water (soluble in hot water) Mechanical properties Impermeability to gases and aromas Weldability Bondability after wetting Electrical surface conductivity Pigmentability Printability Solvent resistance Fat resistance Physiological inertness Biodegradability of the solution Absolutely essential for the proposed use Desirable property
Other properties of Mowiol blown film: Good mechanical values (tear strength, elongation at break, puncture strength) Very good solvent resistance Very good resistance to oils and fats High impermeability to oxygen and nitrogen, up to about 50% relative humidity (see Section E 4 ) Good printability without pretreatment of surface Good pigmentability
Oi
Low electrostatic charge build-up without special after-treatment Good weldability and bonding. Table 1 shows the possible applications of Mowiol blown film and its properties [2, 3, 4].
Literature [1] A Harrus, W Zimmermann, Hoechst AG/Resin News 15, 33 (1979) [2] Hoechst AG, EP 0 050 288 [3] Hoechst AG, EP 0 049 483 [4] A Harrus, W Zimmermann, Hoechst AG/Resin News 16, 31 (1980)
G 11
Ind
De
Fil
us
ar
ys
ot
al
ec
to
Uses of Mowiol
G 1.6.3 Injection moulding Another application for the Mowiol-plasticizer blend produced as described in Section G 1.6.1 is the thermoplastic production of injection mouldings of all kinds. Partially hydrolysed, lowmolecular Mowiol grades in particular are used for the purpose, eg Mowiol 4 88 and 5 88 alone or in combination with other Mowiol grades and plasticizers. Polystyrene masterbatch can be added to the blend to colour it. Injection moulding can be used to produce water-soluble articles that rot away naturally after use. As Mowiol blend tends to shrink, the injection moulds should be of a conical design, if possible. In injection moulding, as an extrusion, the following conditions should be oberserved: Smallest possible volume of material heated in the cylinder Short dwell time of blend in cylinder Heating 145 190C Injection pressure 100 130 bar.
Literature Hoechst AG, Feistel GmbH & Co. KG, Gllheim, German Federal Patent 2 714 545
G 1.8
Solvent-resistant Dip-coated Mowiol Articles
Because of its resistance to most organic solvents (see Section E 5), especially chlorinated hydrocarbons, Mowiol is suitable for the manufacture of protective clothing such as solvent-resistant gloves and aprons. The main grades used are Mowiol 888, 1888 and 2688. To obtain supple films, it is advisable to include a plasticizer in quantities of up to 50% by weight, relative to Mowiol. The choice of production process depends on the mechanical stress exerted on the parts. Very stable products can be made by dip-coating or surface-coating textile fabrics. It is advisable to apply a primer first, eg Mowilith DM 37 approx 55%, and coat with Mowiol afterwards. The best form of application is multiple dipping or brushing with intermediate drying, since a smooth surface can be obtained only by slow drying of a thin film. Because of the viscoplastic properties of Mowiol films, such articles can also be produced without a textile backing. In this case the mould is dipped into the Mowiol solution. The film is produced by careful drying and rotating in a screw fashion in a circulating air heating duct. The film thickness is determined by the solids content and viscosity as well as by the number of applications from solution. The protective clothing, etc, can be waterproofed to some extent by subsequent dip-coating in acidified formaldehyde solution. This treatment should never be more than superficial as it tends to stiffen the products. Solvent-resistant protective clothing can also be produced with cold-water-insoluble Mowiol blown films (see Section G 1.6). This is attached to textiles by heat sealing or lamination.
G 1.7
Mowiol in Protective and Strippable Coatings
Objects requiring protection from mechanical damage or attack by aggressive non-aqueous media during transport or storage can be covered with a coating of Mowiol. Depending on the degree of water-resistance required, the recommended Mowiol products are the low-to medium-viscosity, partially hydrolysed grades (easy to wash off with cold water) or medium-viscosity, fully hydrolysed grades (resistant to cold water). The Mowiol solution is applied by dip-coating, brushing or spraying. Mowiol has relatively good adhesion to certain substrates. When used in strippable coatings for such substrates it needs an addition of adhesion reducer. The products PAT 662 / B produced by Wrtz / Bingen and the Clariant waxes KPE and KLE have proved effective for the purpose. The waxes are used as 10% aqueous emulsions. The addition of silicone oil can also help to reduce the adhesion of Mowiol films. The nature and quantity of these added substances determine the degree of adhesion. Sometimes the polymer has to be platicized. Various pigments or water-soluble dyes can be incorporated.
G 1.9
Mowiol as Release Agent for Casting and Laminating Resins
Unsaturated polyester resins (eg Alpolit) or epoxy resins (eg Beckopox) produced by Vianova Resins usually reinforced with glass fibre matting, are cured in moulds (eg for boat hulls) at normal to elevated temperatures. The adhesion of glass-fibre-reinforced plastic (GRP) to the mould must be as low as possible in order to allow rapid mould release.
G 12
Uses of Mowiol
% Percentage solvent in solution 100 80 60 40 g f e 20 d c b a a b c d e f g water ethanol : water = 10 : 90 ethanol : water = 20 : 80 ethanol : water = 30 : 70 ethanol : water = 40 : 60 ethanol : water = 50 : 50 ethanol : water = 60 : 40
50
100
150
200 Minutes
Figure 5 Drying rate of Mowiol 4 88 solutions, 10% in water and water/ethanol mixtures, temperature 35 C (Ultra-X dryer)
% Percentage solvent in solution 100 80 60 40 e d c 20 b a a b c d e Water isopropanol : water = 10 : 90 isopropanol : water = 20 : 80 isopropanol : water = 30 : 70 isopropanol : water = 40 : 60
50
100
150
200 Minutes
Figure 6 Drying rate of Mowiol 4 88 solutions, 10% in water and water/isopropanol mixtures, temperature 35 C (Ultra-X dryer)
G 13
Uses of Mowiol
m Pa . s 100 90 80 70 60 50 40 30 20 10 0
Viscosity
Mowiol 4-88
The release agents used are solutions, preferably of Mowiol grades 488, 888 or 1888, with 30 to 10% solids content. The viscosity of the Mowiol grades and the concentration chosen determine the thickness of the release agent coating. To increase the flexibility of the Mowiol film, up to 15% plasticizer, relative to Mowiol, can be added to the solutions. As the Mowiol solutions cannot generally be made up to a solids content exceeding some 30% a considerable quantity of water has to evaporate in order to form a film. This process can be accelerated by the addition of low-molecular alcohols. The quantity depends on the Mowiol grade and type of alcohol used. Compatibility decreases in the order: methanol, ethanol, propanol, etc. It is best for Mowiol products with a low degree of hydrolysis. Low viscosity also benefits the alcohol compatibility, ie Mowiol grades such as 383 as well as Mowiol 488, 888 and 1888, are highly suitable for the production of release agent solutions. The limit of alcohol compatibility is indicated by incipient turbidity in the Mowiol solution. The reduction in Mowiol release agent drying time which can be achieved in this way makes a great contribution to the cost-effectiveness of GRP manufacture. Figures 5 and 6 show the drying rates of 10% Mowiol 4 88 solutions as a function of solvent content. The incorporation of ethanol or isopropanol, for example, into the existing Mowiol solution is accompanied by an increase in viscosity (Figure 7) which can have a beneficial effect on processing.
Mowiol precipitates
90 10
80 20
70 30
60 40
50 50
Water % 40 30 60 70 Ethanol %
Literature Ptz, Industrie-Lackier-Betrieb 38, 226 (1970)
Figure 7 Viscosities of 10% Mowiol 4 88 solutions in water/ethanol mixtures, measured in a Hppler viscometer at 20 C Mowiol in aqueous solution either coated or sprayed on or in the mould offers the following advantages as a release agent: Good film-forming with no cracks Anti-adhesive release effect even when applied thinly Impermeability to the organic compounds used, eg styrene Possibility of removing residual Mowiol on the surface of the GRP moulding with water. Mowiol films (see Section G 1. 6) are also used for lining the mould for special casting resin techniques.
G 1.10 Production of Detergents and Cleaning Agents with Mowiol

For reasons of convenience and economy, the active materials used in liquid detergents and liquid cleaning agents are usually marketed in diluted form. Despite the high water content, adequate viscosity is required in the mixture so that the active substances do not run off too quickly, eg from vertical surfaces. Mowiol has proved valuable as a thickener and shine-enhancing agent. It is compatible with detergents and other additives such as ammonia and organic solvents in the required concentrations and also supports the surfactant effect of these substances (see Section D 4). The foam-stabilizing effect of partially hydrolysed Mowiol grades is especially useful in the formulation of cleaning agents for beer glasses.
G 14
Uses of Mowiol
As already mentioned, industrial and floor cleaners are usually made alkaline by the addition of ammonia and may contain organic solvents (such as isopropanol). The appropriate Mowiol products for this application are the fully hydrolysed high-viscosity grades. A special combination of cleaning agent and strippable coating comprising a Mowiol solution and emulsifier is used as a record cleaner. Lavatory cleaners contain amidosulphonic acid. Liquid products available commercially have a high viscosity. Here again the consistency of the solution can be adjusted after it is made up with aromatics by adding fully hydrolysed high-viscosity Mowiol grades. It is recommended that formalin be added because of its germicidal action. In the acid pH range it produces high viscosity in the cleaning solution by forming acetal with Mowiol. Cleaning jellies and pastes can also be produced in this way.
G 1.12 Mowiol in the Metal Industry

G 1.12.1 Secondary brightener in electroplating To impart a shine to applied metal layers of zinc, cadium, nickel, tin, etc [1], the electroplating industry adds brighteners to the plating bath. The term primary brighteners covers various organic compounds, eg aldehydes (anisaldehyde, benzaldehyde, cinnamic aldehyde) or betaines [2], eg of quaternary aromatic N-heterocyclics. The shine is greatly enhanced if Mowiol is added as a secondary brightener [3, 4, 5]. It is also important for Mowiol products to be compatible with the ions in the plating bath, and it is essential to minimize any change in the polymer when current is passed through. The ion compatibility of various Mowiol grades was tested on a model scale with respect to caustic soda in a concentration of 200 g NaOH/I by intermixing equal volumes of NaOH solution and Mowiol solution of the specified solids content at 20 C:
G 1.11 Mowiol in Plant Protection Agents

Plant protection agents are used both in solution and in dispersed form. They must adhere for as long as possible to the plant they are used to protect. The addition of Mowiol significantly improves the adhesion of the plant protection agent to leaf and flower surfaces, which are usually hydrophobic, by film formation after drying. Mowiol has the advantage of showing no phytotoxic effects (Mowiol 488, 1888, 2899) have been tested for phototoxicity on various young cultivated plants. In dispersed or dispersible plant protection agents Mowiol also acts as a protective colloid and prevents sedimentation of the active ingredient. Partially hydrolysed Mowiol grades are preferred both to improve adhesion and as a protective colloid additive; they are used in quantities of 1 2 % relative to the mixture. To avoid contact with the skin and mucous membrane, plant protection agents in powder form are now filled into portion packs made of cold-water-soluble Mowiol film (see Section G 1.6). The film of these packs forms an integral part of the product, ie when dissolved it also acts as a protective colloid and sticker.
Solids content Mowiol 3-83 Mowiol 4-88 Mowiol 4-98 Mowiol 10-98 + good compatibility
1% + + +
2% + + +
3% +
4% +
5% +
turbidity
In practice, however, the plating baths are usually heated to 50 60 C. As a result the compatibility of Mowiol solutions with ions decreases, as shown by the following table for a test at 60 C: Solids content Mowiol 3-83 Mowiol 4-88 Mowiol 4-98 Mowiol 10-98 1% + + 2% + 5% + -
The compatibility of the polymer with respect to the relatively high concentrated caustic soda solution can be assessed only in a small-scale experiment. Mowiol 383 and 488 proved to be most suitable. In practice, bright plating baths contain Mowiol in quantities of less than 2% and also differ considerably in their composition. Therefore, in addition to the Mowiol grades listed above, highermolecular products such as Mowiol 888 and 1888, 498 and 1098 can be used.
G 15
Uses of Mowiol
Literature [1] H J Barrett, C J Wernlund, US Patent 2 211 251 [2] J D Rushmere, DOS 1 496 965 [3] H J Barrett, C J Wernlund, US Patent 2 171 842 [4] R Weiner, German State Patent 688 155 [5] G Senge, G Voss, German Federal Patent 2 525 264
A filling compound has to satisfy the following requirements: Good wetting of the substrate during application Firm adhesion to the substrate after drying Good processability, ie tack (no rolling) during application Rapid through-drying
G 1.12.2 Quenching baths for steel No shrinkage-cracks The choice of quenching medium has a considerable effect on the hardening of steel. The aim is to achieve uniformly rapid cooling throughout the cross-section of a workpiece. Where cooling is uneven, alloyed steels in particular tend to develop cracks, although these can be reduced by the use of an appropriate quenching medium. Quenching agents for tempering steel include solutions of Mowiol 4088 or 1098, for example. The Mowiol concentration of the aqueous quenching liquid is 0.02 to 0.5% by weight, the most convenient method of preparation being from a Mowiol stock solution. Quenching is performed in an immersion-hardening tank or by using a spray system. As some of the Mowiol is decomposed during the process, it is advisable to monitor the concentration of the immersion bath, eg by checking the refractive index (see Section D 2.1) or the density (see Section D 2.2). Another advantage of using Mowiol in this sector rather than other substances is that it involves no risk, being non-combustible and non-toxic.
Literature P E Cary, E O Magnus, W E Herring, Metal Progress 79 (1958) K H Kopletz, Werkstatt-Technik 54, 293 (1969) S Segerberg, J Bodin, Metallurgia 9, 425 (1986)
Formation of hard, but not brittle, coating No clogging of sanders during rubbing-down of the coating Good adhesion of subsequent coats (paint) on the sanded coat filling compound. Filling compounds that meet these requirements can be formulated on the basis of Mowiol 4 88 or other, preferably partially hydrolysed Mowiol grades. These binders are soluble in water but inert to organic solvents, so that in subsequent painting the filling compound is unaffected (no softening, swelling or lifting). The cold-water resistance of the dried filling compound can be improved by using calcium hydroxide to saponify the residual groups of the Mowiol used, followed by neutralization with sulphuric acid [1]. The compound is prepared in a kneader. After dispersants and wetting agents are incorporated into the pigment/filler mixture, a plasticized Mowiol solution containing preservative is added and homogenized. Optimum matching of the grain sizes of the filling compound mixture (eg different kinds of chalk) in the compound is important for crack-free drying, especially in thick layers. Uses for Mowiol roller-applied filling compounds: Application by machine on wood surfaces (solid wood, plywood, chipboard), plaster, plasterboard, polystyrene foam, asbestos cement, etc.
G 1.13 Mowiol in the Paint Industry

G 1.13.1 Roller-applied filling compounds Filling compounds, including those applied by roller, are used for surface preparation prior to painting where the appearance needs to be of a high standard. In the furniture industry, for example, the filling compound is applied by machine and then sanded before painting. Filling compounds can broadly be classified as coatings. They are usually applied in a relatively thick layer.
Literature [1] Hoechst Aktiengesellschaft, German Federal Patent 2 557 557
G 16
Uses of Mowiol
G 1.13.2 Wood primers An important prerequisite for the manufacture of a wood primer is a binder providing the following properties: Low viscosity, to obtain systems with a high solids content and good processability Good wetting of the substrate and good penetration to achieve optimum adhesion Characteristics that allow the wood to breathe A good key for subsequent paint coats of various compositions, which need to adhere well to the primer without softening or lifting it. These conditions are ideally satisfied in wood primers based on Mowiol, especially Mowiol 383 as the grade with the lowest viscosity. Water-based primers of this kind can be diluted with alcohol, so that the drying rate can be varied to some extent (see Section G 1.9). Wood primers with Mowiol as binder can be rated physiologically and ecologically as very safe.
Powder-type distempers containing Mowiol and pigments cannot be produced on the side simply by stirring the Mowiol granules in cold water, because the water needed to dissolve the Mowiol has to be hot. Mowiol/pigment compositions can be produced by a simple method [1] that involves converting the relatively highly concentrated distempers (20 30 % water content) into a solid form in a dryer. Depending on the drying equipment used, the distemper will take the form of flakes (roller dryer, belt dryer) or powder (spray dryer). The small proportion of homogeneously distributed Mowiol in the dry distemper composition ensures that the dry paint prepared in this way can be repidly mixed in cold water to the desired consistency. The partially hydrolysed Mowiol grades are particularly suitable as binders in such cases. The process for the production of dry Mowiol / pigment compositions is equally suitable for the production of watercolours.
Literature [1] Hoechst Aktiengesellschaft, Austrian Patent 315 987
G 1.13.3 Distempers and watercolours Mowiol has high pigment-binding power and is used as a binder for distempers and watercolours. For the same equally good dry rub resistance the quantity of binder can be between 1% (high viscosity Mowiol grades) and 5% (low-viscosity Mowiol grades), relative to the dry paint. Low-viscosity Mowiol grades are preferred when the washablility of the paint coating is important. To produce a liquid distemper with Mowiol as binder, the pigments are stirred into the prepared Mowiol solution (care being taken to prevent foam formation). Agitan 295 is recommended for use as a defoamer. The paint is preserved with the products described in Section D 3. 2. Mowiol-bound paint has the following advantages over cellulosebound distempers and watercolours: Good workability Good dry rub resistance Suitability for application over soiled paint without causing softening Production of water-washable coatings. The cold-water resistance of the coating can be improved (see Section 1.13.1). G 1.13.4 Emulsion paints Mowiol can be used instead of cellulose derivatives to modify emulsion-bound paints and plaster systems. Mowiol improves the workability, lengthens the open time of the coating because of its good water retentivity and reduces the risk that the paint will be rapidly deprived of its moisture then used on highly absorbent substrates. Mowiol as thickening agent can also help to regulate the consistency of paint and plaster. Mowiol's good protective colloid effect improves mechanical stability in many emulsion binders, stability in dry pigmentation and compatibility with other additions such as solvents, defoamers and preservatives. This property is particularly important in the formulation of paints and plasters. The high-molecular, partially hydrolysed grades are particularly suitable for use in the paint industry, eg Mowiol 1888, 2688 or 4088 and, for high water-resistance in the paint-film, Mowiol 2899. Mowiol should be used as an aqueous solution. The details given in section C 3 should be observed in its preparation. Depending on the degree of polymerization, it is advisable to prepare a suitable highly concentrated stock solution (see section D 2).
G 17
Uses of Mowiol
G 1.13.5 Artist's pastes / finger paints Binders for finger paints must be physiologically inert. Mowiol is suitable for this application when used in combination with glycerine as plasticizer. Polyvinyl alcohol can be used if the aqueous solution satisfies the purity requirements of the BgVV (Federal German Health Office Recommendation) XLVII / Toys, eg minimal organic solvent content. The instructions in Chapter F / Section F 1 (Safety at work) must be observed. The usual grade employed is Mowiol 488 because of its low viscosity. Careful matching of the pigments, fillers and inorganic thickening agents is necessary to construct the right property profile for the paint. Defoamers and preservatives used must satisfy the relevant national statutory provisions on physiological safety.
These applications make particular use of its high compatibility with such materials as pigments and wetting agents, as well as its ability in aqueous solution to form tough, elastic, watervapour-permeable films, which adhere to the skin but can be peeled off. The purity of the polyvinyl alcohol solution used here has to satisfy statutory requirements. The instructions in Chapter F / Section F 1 (Safety at work) must be observed. In eyeliners, fully hydrolysed Mowiol grades are used as binders for fillers and pigments. For face masks that are easy to remove it is advisable to use Mowiol grades from the medium to high viscosity range. Physiologically inert plasticizers suitable for modifying the consistency include glycerine and poyglycols. Wetting agents and skin preparations (camomile extract, allantoin, honey, aqua hamamelis, vitamin oils) can also be incorporated into the 5 10% Mowiol solutions. The skin creams made with Mowiol offer protection against oils, lubricants, fats, tar, metal dust and organic solvents. As well as wetting agents, formulations contain glycerine plasticizers and magnesium or aluminium oxychloride as moisture-retaining agent. Medium-viscosity, partially hydrolysed Mowiol grades are preferred. The main constituents for hand cleaning pastes are active detergents and alcohols in combination with Mowiol.
G 1.14 Mowiol in the Building Industry

Additions of small quantities of Mowiol in powder form improve the processing properties in trowelling compounds, building adhesives and plasters. Such additions to mixes of building materials provide the following advantages: Improved cohesion in the compounds Good adhesion of mortar to mineral substrates Reduced sticking of mortar to applicator tools Easier smoothing Reduced formation of shrinkage cracks. Low-molecular, partially hydrolysed Mowiol grades in the form of fine powders are preferred. The quantity added is about 0.1%, relative to the dry mortar mix. The added Mowiol is activated when the mortar is made up with water.
Literature [1] Lexikon der Hilfsstoffe, Polyvinylalkohol [2] M Grimberg, Seifen - le - Fette - Wachse 24, 815 (1963)
G 1.16 Fluorescence Analysis

Mowiol is used as an embedding and fixing in analytical investigations using immunofluorescence. Mowiol 488 is the standard grade employed [1]. Mowiol is used as a pellet matrix in X-ray fluorescence analysis of rock samples.
G 1.15 Mowiol in Cosmetics

Because of its good water solubility and excellent film-forming properties, its effectiveness as a thickening agent and physiological acceptability, Mowiol can be used in cosmetics [1] for such applications as: Eyeliners Face masks Skin creams [2] Hand cleaners (abrasive and peel-off pastes).
Literature [1] J Rodriguez, F Deinhardt, Virology 12, 316 (1960) H Beug, M Claviez, B M Jokusch, Th Graf, Cell 14, 843 (1978) H Beug, A v Kirchbach, G Dderlein, J-F Conscience, Th Graf, Cell 18, 375 (1979) E Harlow, D Lane, Antibodies, a Laboratory Manual, Cold Spring Harbor Lab, S. 418 (1988) P C Dartsch, Labor-Medizin 12, 565 (1989) P C Dartsch, Labor-Medizin 9, 450 (1990)
G 18
Uses of Mowiol
G 1.17 Microencapsulation
There are many methods of microencapsulation: mechanicophysical or chemical, and encapsulation by coacervation. In this way, substances such as solvents, water, adhesives, pharmaceuticals, vitamins and enzymes, liquid crystals, aromas and perfumes, fertilizers and plant protection products can be converted into a dry substance, the contents of which can be released when needed by thermal, mechanical, chemical or enzymatic action. Polyvinyl alcohol has many uses in this sphere of application. One important application for microcapsules is NCR papers with polyvinyl alcohol as co-binder for the capsule dispersion. The partially hydrolysed Mowiol grades used are from the low and medium viscosity range.
Literature W Sliwka, Angew. Chem. 16, 556 (1975)
G 2 Applications based mainly on the Reactivity of Mowiol

G 2.1 Acetalyzation / Polyvinyl Butyral / Mowital B
In the presence of mineral acids, polyvinyl alcohols and aldehydes form polyvinyl acetals (see structural formulae below), whereas with ketones they produce polyvinyl ketals, which are less important in industrial terms.
CH2 CHOH O C H
Formation of Polyvinyl acetal
G 1.18 Replicas (Plant Physiology)

Mowiol has no phytotoxicity. This fact and its substrate-friendly film properties enable it to be used to produce stomata replicas (Mowiol 2098; see also title page to Chapter F and Section G 1.11).
Literature E Frank, R Pohl, Naturwiss. 15, 453 (1965) H Metzner, Pflanzenphysiologische Versuche, S. 144/5 (1982)
CH2 CHOH CH2 CH2 HC CH2 HC CH2
H+
O C O H R + H2O
G 1.19 Preservation and Restoration

The products used here for the purpose of preserving works of art and cultural assets have to meet especially high requirements as regards the material properties. Ease of application, adequate adhesive and bond strength, light fastness and reversability are important criteria. Mowiol fulfils these conditions. Because of its good penetrating power and adhesion it has a stabilizing and binding action on porous, loose substrates, fibres and flat materials. For the wide variety of possible materials, Mowiol is used as sole binder or to modify polymer emulsions. The products mainly used are polymers in the partially hydrolysed range.
Among the polyvinyl acetals the polyvinyl butyrals are the most important. They are produced by reacting the polyvinyl alcohol with n-butyralhyde and include the various Mowital B grades [1]. A number of industrial processes are commonly used for the purpose:
G 19
Uses of Mowiol
a. In acetalyzation in an aqueous medium, polyvinyl alcohol, butyraldehyde and acid, dissolved in water, are intermixed and stirred. The polyvinyl butyral produced is precipitated in powder form. b. In acetalyzation in organic solvents (ethanol, ethyl acetate) the polyvinyl alcohol is suspended in the reaction solution containing butyraldehyde and acid. The Polyvinyl butyral produced goes into solution in the reaction. The reaction product is obtained by precipitation. The properties of the polyvinyl acetals produced depend on the degree of acetalyzation, on the molar mass and residual acetyl content of the polyvinyl alcohol and on the aldehyde and acid catalyst used. Statistically, the degree of acetalyzation cannot exceed 86.5% by weight, as the aldehyde can only ever react with two adjacent hydroxyl groups [2, 3]. There are many applications for polyvinyl butyrals (Mowital B). They can be used, for instance, as paint binders or binder components (foil laquers, cold-curing clear varnishes, stoving enamels). They can also be used for printing inks, as well as wash and shop primers. One important area of application for Mowital is as the intermediate layer in laminated glass sheets (sandwich type). Polyvinyl formals are less important in industrial terms than polyvinyl butyrals. They are usually produced by reacting polyvinyl acetate with formaldehyde in the presence of a mineral acid in aqueous solution, using a two-stage process. The formation of polyvinyl formals is caused delibarately and put to use in some Mowiol applications (see Sections G 1.8, G 1.10, G 2.2, G 2.3). Many production processes using aldehyde mixtures are also described in the literature [4].
Literature [1] Clariant brochure Mowital B Polyvinyl butyral (1997) [2] Y Sakaguchi, Review on High Polymers (Japan) 10, 46 (1953) [3] Flory, J. Amer. Chem. Soc. 61, 1518 (1939) [4] Houben-Weyl, Vol XIV/2, 721 (1963)
Depending on the intensity of the cross-linking reaction (acetalyzation) in the precipitating bath, polyvinyl alcohol fibres can be produced with varying degrees of hydrophilicity from watersoluble to slightly swellable. Provided that physiological inertness is assured, water-soluble polyvinyl alcohol fibres can be used for surgical sutures if their absorbability is enhanced by suitable additives [5 12]. Long-chain grades with zero, or at most minimal, acetyl group content, are preferred for boiling-resistant textile fibres spun from polyvinyl alcohol [13 15]. Not only have boiling-resistant fibres been developed; so, too, have fibres with an adhesive action and such soluble in hot water [16].
Literature [1] Austrian Patent 135 162 [2] Austrian Patent 140 461 [3] Austrian Patent 142 693 [4] German State Patent 685 048 (Chem. Forschungsges. mbH) [5] European Patent 552 013 [6] European Patent 420 052 [7] German State Patent 748 317 [8] European Patent 431 776 [9] German State Patent 703 050 [10] H I v Brandis, Zentralbl. f. Chirurg. 63, 372 (1936) [11] W Knig, Zentralbl. f. Chirurg. 63, 377 (1936) [12] German State Patent 699 516 [13] German Federal Patent 1 022 750 [14] F Kainer, Polyvinylalkohole, Verlag Ferd. Enke Stuttgart, S. 111 - 125 (1949) [15] M M Zwick, J A Duiser, C van Bochove in C A Finch Properties and Applications of Polyvinyl Alcohol, Monograph No 30, Soc. Chem. Ind. (1968) [16] German Federal Patent 1 034 477
G 2.3 Mowiol Sponges

Sponges are produced by applying a foaming process to solutions of medium-viscosity, preferably partially hydrolysed Mowiol grades, eg Mowiol 1888 [1]. This yields high-quality sponges with good abrasion resistance, mechanical stability and resistance to chemicals. There are various methods of foaming: a. Entrainment of air with a high-speed agitator b. Homogeneous incorporation of ultra-fine solids particles which give off gases in a chemical reaction c. Incorporation of chemical compounds which can be dissolved out again with water after a given period (eg Tylose, starch, polyethylene glycol and polyacrylamide) [2].
G 2.2
Spinning and Hardening of Fibres
The polar chain structure of polyvinyl alcohol allows the production of staple fibres and filament yarns with good textile engineering properties. For W O Herrmann and W Haehnel (see Section A 1) this area of application was therefore an obvious additional field of study [1 4]. The process of wet spinning from aqueous polyvinyl alcohol solutions into a precipitating bath was first proposed at that time; this process is still the preferred method abroad for the large-scale production of polyvinyl alcohol fibres.
G 20
Uses of Mowiol
In process a., Mowiol 1888, 20% in water, is dissolved as described in Section C 3. After cooling at least down to 20 C or below, air is incorporated into the solution by means of a high-speed paddle stirrer. It is important to cool the solution because this gives better foam stability and a more even sponge structure. The incorporation of air produces a substance with the consistency of stiff cream. By adding formaldehyde in solution or in the form of paraformaldehyde, as well as hydrchloric or sulphoric acid, the conditions for the formalyzation of the Mowiol and thus the formation of the sponge are created. The properties of the mixture can be modified by adding Resamin HF 450 or Aerosil, for example, or even wetting agents such as Hostapon T solution. The latter affects pore stability, regularity and size. After the finished mixture has been poured into a acid-proof (eg Polyolefin) container, it is left to stand for 1 3 days at room temperature and constant humidity. During this time the formalyzation of the Mowiol takes place, an open-pored sponge structure developing within the first few hours. The humidity of the air, the temperature during standing, the quantity of wetting agent added and the nature and length of stirring all have a great effect on the pore size of the sponge. The optimum formulation and production process must be determined in each individual case. After hardening, the sponge is taken from the mould and cleaned free of acid and formaldehyde by squeezing, neutralization, repeated washing and centrifuging. It can be cut into the desired shape by band knives.
In process c., formaldehyde and acid are added to a solution of Mowiol 1888, these two additions being followed by Tylose, degraded starch, polyethylene glycol or polyacrylamide, for instance. After the curing process, a structure develops from which these auxiliary substances can be dissolved out again by hot water. In each of the processes described it is possible to modify extensively the properties of the resultant sponges by adding auxiliary substances. Thus the incorporation of fibres produced from substances such as polyvinyl alcohol or cellulose makes the sponges softer to the touch and increase their absorbency. A softer version of the dried sponge can also be obtained by adding protein components, eg nucleic acids, or vinyl acetate/ ethylene copolymer emulsions, eg Mowolith DM 105, DM 130 or DM 131, to the basic mix [3, 4]. Sponges made of formalyzed Mowiol are completely insoluble in water. Swelling makes them soft and supple. Unlike natural sponges , the synthetic sponge has very high rub-resistance and mechanical stability. It is also rot-resistant. Polyvinyl formal sponges are used as domestic and bath sponges, among other applications. Acetalyzed PVAL foams are also used as aids in the surgical and orthopaedic sectors, eg as supporting dressings. In medicine these open-celled mouldings are occasionally used to cover wounds and for special investigations [5, 6, 7, 8]. When Mowiol sponge dries out, it loses its suppleness in a reversible process and hardens. By incorporating corundum or silicon carbide in the casting compound, it is therefore possible to use Mowiol sponges as abrasive sponges. By (subsequent) curing of the sponge with dilute aqueous solutions of urea or melamine formaldehyde precondensates (eg Madurit MW 3816) the swellability can be suppressed. The resulting products are suitable as filters for gases and liquids.
In process b., foaming is produced not by stirring, but by the development of gas during the curing period. Fine aluminum powder is incorporated evenly into a 20% solution of, for example, Mowiol 1888. When formaldehyde and acid have been added, the mixture is poured into a large acid-resistant mould. After a time a reaction takes place between the acid and the aluminium powder, the resultant hydrogen gas causing the slowly curing mixture to foam. Skilful control of the formalyzation reaction and the development of the gas produces an absorbent, open-pored Mowiol sponge.
Literature [1] H Schindler, Hoechst AG/Resin News 9, 22 (1975) [2] Hoechst AG, German Federal Patent 2 410 848 [3] Hoechst AG, US Patent 4 296 210 [4] Hoechst AG, European Patent 0 079 501 [5] TH L Schofield, The Brit. J. of Surgery, S. 618 (1955) [6] L Riedler, F Sto. Akt. Chir. 18, 132 (1983) [7] P B Boulos, SJ Stryker, RJ Nicholls 71, 213 (1984) [8] L F Fajardo, J Kowalski, HH Kwan, SD Prionas, AC Allison, Lab. Investig. 58, Nr. 6, 718 (1988)
G 21
Uses of Mowiol
G 2.4
Consolidation of Nonwovens
G 2.4.2 Textile nonwovens The finishing processes described for glass fibre nonwovens [1] also apply in principle to the treatment of textile nonwovens. It is best to use partially hydrolysed Mowiol grades in order to achieve better bonding of the binder with the fibre. Particularly good results are obtained with nonwovens based on synthetic fibres.
G 2.4.1 Glass fibre nonwovens Most glass fibre nonwowen material today is used as the core material in the manufacture of bitumenized roofing felt or as the backing for PVC coverings. The inorganic fibre is completely rotproof and therefore superior to the paper felt used previously. The requirements imposed on the nonwovens binder are correspondingly high [1]. The required properties of the two constituents of the nonwoven fibre and binder are classified in DIN 52 141 (Glass fibre nonwovens as a reinforcing material for roofing and sealing sheeting / Definition, Designation, Requirements). The relevant test methods are described in DIN 52 142 (Glass fibre nonwovens as a reinforcing material for roof and sealing sheeting Testing). Other relevant DIN standards are No 51 143 (Bitumenized glass fibre nonwoven roofing material / Definition, Designation, Requirements) and 52 123 (Roofing board and bare board testing methods). The binder property profile laid down in these standards is ideally fulfilled by several Mowiol grades. Mowiol 28 99 (medium viscosity, giving film with low cold-water solubility) is particularly suitable for this area of application. The polymer is precipitated onto the glass fibre from aqueous solution or in the form of swollen particles and gives the nonwoven the desired high tear strength. The heat stability and hot-water resistance of the bonded glass fibre nonwoven can substantially increased, if necessary, by adding water-soluble urea, phenolic or melamine formaldehyde resin precondensates (eg Madurit MW 3816) to the Mowiol finishing liquor. By acid catalysis or the use of elevated temperatures these products also condense with the functional groups of the Mowiol and thus yield three-dimensionally cross-linked polymers. The proportion of Mowiol to Madurit can be varied within wide limits. Even a 5 : 1 mixture produces a noticeable effect in terms of the strength and thermal stability of the bonded glass fibre nonwoven. As the proportion of Madurit increases, so, too, does the stiffness of the finish. Hydrophobic nonwovens can be obtained with the above resin combination by adding small quantities of special polysiloxane compounds. Another way of increasing the water-resistance of Mowiol-bonded nonwovens is to subject them to such high thermal loads during the drying phase that the Mowiol hardens to a horn-like consistency. As a result the binder becomes hydrophobic.
Literature [1] Hoechst Aktiengesellschaft, German Federal Patent 2 110 612
G 2.5
Photosensitive Coatings
Offset Printing Plate Coatings / Printing-Screen Lacquers / Colour Television Screens
Photosensitive coatings consist of a film-forming agent and a sensitizer. The film-forming agent determines: The mechanical and physical properties of the coating (adhesion to the substrate, strength and stability) The nature and quantity of the stabilizer The treatment of the system in exposure and development The gradation of the print. The original film-forming agents used were colloids of animal or vegetable origin (albumen, gelatine, fish glue, polysaccharides) [1]. Modern systems are based on polyvinyl alcohol [2]. The question of whether a high- or low-viscosity Mowiol is used depends on the requirements arising from the various applications. Mowiol from the low-viscosity range is used if thick coatings are to be produced economically. If good gradation takes priority, it is advisable to use a higher-viscosity grade. Mediumviscosity Mowiol represents a good compromise. The sensitizer is normally produced as a separate solution which is added to the film-forming agent shortly before application of the system to the substrate. In other words, after the filmforming agent and sensitizer are intermixed there is a limited processing time which can be varied by adjusting the pH. In practice there are also one-pot systems in which the film-forming agent and sensitizer are ready-mixed. Preference is given in this case to Mowiol 20 98, as the set pH is not affected by subsequent saponification of the residual acetyl groups present in the polymer molecule.
G 22
Uses of Mowiol
The finished mixture is applied to the substrate by centrifuging, doctor coating or other methods. Ammonium dichromate or special diazonium compounds are used as photosensitizers for Mowiol. The mechanism for photocuring Mowiol by dichromate is based on the light-induced oxidation effect of Cr+6. The Cr+3 which is produced forms complexes by way of OH groups of the film-forming agent Mowiol [3, 4]. This reaction causes a reduction in the water-solubility of the exposed areas of the coating. Slight reduction of the dichromate is also possible by infrared radiation (heat). Sensitized solutions of Mowiol or plates coated with it must therefore be stored in a cool place to prevent a reaction in darkness. Diazo-sensitized coatings are easier to handle in this respect, but here again it is advisable to observe certain storage conditions. The commercially available special diazonium compounds are stable for long periods at room temperature. Only when exposed to short-wave light (maximum absorption between 300 and 450 nm) does photolytic cleavage of the N-N arrangement take place in the molecule, followed by the substitution of hydroxyl groups. As a result, the decomposition products produced in this way are able to form water-insoluble complexes with Mowiol. The mixture whose composition and action have been described are used for the production of printing plates, screens for screen printing, scanned-image screens (eg colour television tubes) and boards for printed circuits [5]. An effective means of exposing the coating through a negative or raster negative is to use carbon arc, xenon or high-pressure mercury vapour lamps. Developement is then carried out by spraying with hand-hot water, which washes off the unexposed areas. After drying, the stencil is used without further treatment as a screen printing master. In many cases it is advisable to increase the water-resistance of the cured coating by incorporating a polymer emulsion, eg Mowilith D approx 50% DM 1 and DM 2 approx 55% or DM 2 HB approx 53%, into the photosensitive mixture. As a printing forme for offset printing, the stencil needs further treatment. This involves first applying PVC lacquer and then removing the coating, etching, etc [5]. Given the extraordinary precision required in the production of colour television screens, Mowiol is needed not only as a photosensitizable binder for the luminescent pigments, but also as a protective colloid for the pigment particles [6, 7]. The very low extraneous ion (ash) content of the polymer is a crucial factor. The preferred grade of Mowiol is Mowiol 4088.
Solutions of low-viscosity Mowiol grades are recommended as a retouching medium for repairing faults in printing screens. The use of such products allows a high solids content in the retouching media and thus rapid drying of the repaired area.
Literature E Rohaupter and D Hundt, Chemie unserer Zeit, p 147 (1971) H Lee van Nice, Rodney Farlee, Polymer Engg. and Sci. 17, 359 (1977) B Duncalf and A S Dunn, J Appl. Polym. Sci. 8, 1763 (1964) K Schlpfer, Zur Kenntnis der Reaktion zwischen Polyvinylalkohol und sechswertigem Chrom unter besonderer Bercksichtigung der Reaktion in lichtempfindlichen Schichten, Monograph St Gallen (1964) [5] D Schmidt, Metalloberflche 9, 257 (1967) [6] W Mller, farbe + lack 83, 991 (1977) [7] G Bolte, farbe + lack 88, 528 (1982) [1] [2] [3] [4]
G 2.6 Printing Inks for Decor Paper

The laminate papers printed with Mowiol as binder can be used for all melamine and polyester laminates. Mowiol 498 has proved its value as a binder for decor paper printing inks, as is shown by the following comparison of requirements and the property profile of the polymer: The ink binder must be soluble in water / ethanol mixtures. Aqueous Mowiol solutions can be blended with alcohol in the required proportions. After the print has dried it needs to be damp-proof with good resistance to wiping / Mowiol has high pigment binding power. It is possible to manage with small proportions of binder which do not seal off the surface of the paper. In melamine resin impregnation the print should be wetted quickly without starting to dissolve / This is possible with Mowiol 498. In melamine resin sheets, when the whole composite structure is being compressed, there must be not print transfer during the thermal treatment in the condensation phase and therefore no marking-off onto the pressure plates / Mowiol 4 98 is compatible with melamine resin within certain limits (see Section D 7.2.6). Because of the high pigment-binding power and the cross-linkage with the impregnating resin it is even possible to use those pigments which cannot be employed in conjunction with other binders. For polyester laminates the print must be insoluble in styrene/ Mowiol 498 satisfies this requirement.
G 23
Disposal of Mowiol
Polyvinyl alcohol, and hence also Mowiol, is degraded in aqueous solution by adapted microorganisms into carbon dioxide and water. This process is employed in biological purification plants. The electron micrograph shows microorganisms of this type (verticellae) from the activated sludge. Scale of illustration 1140 : 1
Disposal of Mowiol Page
1 2
Wastewater / Biodegradation Recovery (Recycling) and final Disposal
H1 H2
Disposal of Mowiol
H 1 Wastewater / Biodegradation
If Mowiol is not destroyed by incineration to form carbon dioxide and water, Mowiol solutions often have to be discharged into the wastewater system with a biological purification plant downstream. When stored in aqueous solution, polyvinyl alcohol, and therefore Mowiol as well, may be attacked by micro-organisms (see Section D 3.2). This characteristic, though considered a drawback for storage purposes, nevertheless has a favourable effect on its behaviour in biological purification plants, for instance, where Mowiol in solution can be mineralized into carbon dioxide and water by adapted micro-organisms. The biodegradation of fully and partially hydrolysed Mowiol in aqueous solution can be successfully achieved by a simple technique under stationary conditions in the laboratory [1]. Further work has been done in relation to the disposal of watersoluble polymers in wastewater from textile finishing [2]. The illustration below shows the results of biodegradation of Mowiol solutions (Zahn-Wellens-Test). This clearly reveals virtually no difference between fully and partially hydrolysed Mowiol. After a certain time has been allowed for the system to
adapt, biodegradation is increasingly accelerated while quantities with the same chemical oxygen demand (COD) are added continuously. Naturally, the adaptation time is eliminated of its own accord once the micro-organisms present in the activated sludge have become accustomed to polyvinyl alcohol / Mowiol. Not too much importance should be attached to the relatively high COD value of some 1750 mg O2 / g for polyvinyl alcohol compared with other water-soluble macromolecules such as starch, CMC and polyacrylates, since the quantity of Mowiol needed for comparable processing is usually much smaller than the requirement of the other water-soluble polymers mentioned. The correct operation of a biological purification process naturally requires that dissolved Mowiol should not be toxic to the wastewater bacteria. Industrial experience shows in fact that quantities as high as 1g / l to 2.5 g / l are degraded without any harmful effects. Such product concentrations do not normally occur in industrial wastewater. Tests with dilute Mowiol solutions have also shown that sensitive fish varieties (golden orfes and guppies) are not affected even at Mowiol concentrations of 500 mg / l water.
Literature [1] R Zahn and H Wellens, Chemikerzeitung 98, 228 (1974) [2] K Fischer, Melliand-Textilberichte 59, 487, 582, 659 (1978), 65, 269, 340 (1984) and Deutscher Frber-Kalender 84, 326 (1980)
COD (mgO2 /l) 1000
PVAL fully hydrolysed
PVAL partially hydrolysed + Addition of 0,5 g/l PVAL
500
COD of the aqueous phase of the activated sludge suspension
10
15
20
25
30 Days
Biodegradation of Mowiol solutions of partially and fully hydrolysed grades (Zahn-Wellens-Test), adaption of activated sludge (5.6 g / l dry weight)
H1
Disposal of Mowiol
H 2 Recovery (Recycling) and final Disposal

In the recycling process, polyvinyl alcohol Mowiol can be recovered from aqueous solution by filtering and concentration. The concentrate [1, 2, 3] can be re-used or disposed of by being precipitated with salts or complexed [4] and regenerated and / or incinerated or dumped. The final stage, however, may also be to discharge the solutions into the wastewater system with subsequent biological purification (see Section H 1). Finally, concentrated polyvinyl alcohol solutions can be incinerated. There are two possible strategies for obtaining higher PVAL concentrations: To produce more highly concentrated regeneration liquors by using less water and disregarding yield to some extent To concentrate the regeneration liquor. In the former case, either the substrate, eg a fabric, can be impregnated with water and the concentrated solution squeezed out after swelling time, or using a Clariant process the material containing the polyvinyl alcohol can be subjected to normal extraction at 85 90 C, eg washing, although with a reduced amount of water. In this case it is still possible to attain recovery rates of just under 50%. Water extraction rates of some 80% can be achieved (in the textile sector) with high-pressure squeezing units. These processes are known as partial recycling. To concentrate PVAL solutions the following methods can be considered: Evaporation Precipitation and re-dissolving Ultrafiltration The most difficult process is evaporation, for which the engineering costs in particular are considerable. PVAL can be precipitated with iron aluminum salts or as a calcium / boric acid complex (Clariant process), in the latter case even with highly dilute solutions (0.01%) with an efficiency of more than 98%. The precipitate can be recycled with mineral acids into the starting products. The ions are separated by dialysis and the concentrated PVAL solutions can be re-used. Optimum precipitation of polyvinyl alcohol, however, requires an added quantity of boric acid, which is economically and ecologically inadvisable.
This process, too, involves losses, and the operating costs are high. The chemical removal of PVAL could take place, for example, at the end of a recycling process designed to include preliminary cleaning of the concentrated wastewater. In this case the precipitation products would then have to be incinerated. The residual polymer remaining would have to undergo biological degradation (see Section H 1). The incineration of a PVAL solution is also technically feasible. If highly diluted, however, a considerable amount of water has first to be evaporated. With a 30 40% solids content in the solution the incineration process is self-sustaining. With oil firing a solution of this concentration, when added in quantities of 10 20%, can be burned simultaneously without increasing the oil consumption. The thermal energy produced can be used again for the concentration process. With this method the costs are transferred to the evaporation process already mentioned. Ultrafiltration is a separation process for the fractionation of colloid-disperse particles or their separation from the dispersing agent. It is based on the filtration taking place under pressure through modular polymer membranes which are usually in tubular form and permeable to both the dispersing agent and moleculardisperse substances but impermeable to colloids. With this process a polyvinyl alcohol solution is separated into the permeate (water and possibly low-molecular PVAL fragments) and the concentrate. In the total recycling that takes place here, both fractions are returned in full in closed circuits to the processing operation. The ultrafiltration process is now the state of the art. It produces regenerated products which can be re-used time and again for the purpose intended. The re-use of polyvinyl alcohol solutions represents an important method of reducing the quantity of wastewater produced. It is thus of direct benefit to the environment and results in a substantial reduction in material costs. In practice the optimum overall design concept for a modern (textile) plant is probably a combination of partial recycling with subsequent ultrafiltration [5, 6, 7, 8].
Literature [1] O Deschler, Melliand Textilber. 12, 1003 (1979) [2] O Deschler, Melliand Textilber. 1, 42 (1980) [3] O Deschler, Melliand Textilber. 10, 716 (1983) [4] Hoechst AG, (Clariant), US Patent 4 166 033 [5] J Trauter, W. Armbruster, Melliand Textilber. 7, 571 (1980) [6] J Trauter, Textil Prax. Int. 3, 239; 5, 470; 6, 599 (1983) [7] J Trauter, Melliand Textilber. 1, 17 (1990) [8] G. Schmid, Melliand Textilber. 7, 557 (1991)
H2
Imprint
Publisher: Kuraray Specialities Europe KSE GmbH Industriepark Hoechst 65926 Frankfurt/Main Germany
Coated paper containing Mowiol as carrier for optical brighteners has been used for this publication. The information in this publication is based on our present state of knowledge and is intended to provide general notes on our products and their uses. It should not therefore be construed as guaranteeing specific properties of the products described or their suitability for a particular application. Any existing industrial property rights must be observed. The quality of our products is guaranteed under our General Conditions of Sale. Kuraray Specialities Europe KSE GmbH Frankfurt/Main, Germany June 2003
KSE
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D-65926 Frankfurt/Main Phone +49 69 3 05 85300 Fax +49 69 3 05 85399
Commserv, Frankfurt am Main
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Specialized in Specialities

Mowiol History / Manufacture / Structure

The Mowiol Range

Production of Mowiol Solutions

Properties of Mowiol Solutions

The Mowiol Film

Physiological Properties of Mowiol

C 1 2 2.1 2.2 2.3 3 4

R&D Department Kuraray Specialities Europe KSE June 2003

Mowiol History / Manufacture / Structure

Mowiol - History / Manufacture / Structure Page

1 2 2.1 2.2 3 3.1 3.2

Mowiol - History / Manufacture / Structure

A 1 History of Polyvinyl Alcohol

A 2 Manufacture of Polyvinyl Alcohol

Manufacture of Polyvinyl Acetate

CH2 = CH n OCOCH3 Vinyl acetate

CH2 CH OCOCH3 n Polyvinyl acetate

Mowiol - History / Manufacture / Structure

A 3 Structure of Polyvinyl Alcohol

CH2 CH OCOCH3 Polyvinyl acetate CH2 CH OH Polyvinyl alkohol n n

+n CH3OCOCH3 Methyl acetate

Mowiol - History / Manufacture / Structure

a) Acetyl chain branching:

CH2 CH OC=O CH2

Cis-4,6 derivative of m-dioxane

OH CH2 C O C=O CH3 or

Trans-4,6 derivative of m-dioxane

Interaction between Polyvinyl Alcohol Chains

Mowiol - History / Manufacture / Structure

The Mowiol Range

The Mowiol Range Page

The Mowiol Range

The Mowiol Range

B 1.0 Application fields/Survey

Fully hydrolysed types

Mowiol application fields (chapter G in detail)

Main application sectors

The Mowiol Range

Analytical Chemistry of Mowiol

WNa O-ash content = 2 WNa O-ash 2

(VB1 VSa) tNaOH CTitr.Ag. M1/2 Na2O MSa . 10

VB1 VSa tNaOH CTitr.Ag. M1/2 Na O 2 MSa 10

The Mowiol Range

The Mowiol Range

mg KOH/g 700 650 600 500 400

B 2 Water Absorption of Mowiol Granules

20 0 10 30 50 70 90 100 mol% Degree of hydrolysis

B 3 Behavior of Mowiol under the Effect of Temperature

The Mowiol Range

80 100 Relative humidity at 23 C

Figure 2 Water absorption of partially hydrolysed Mowiol grades in granular form

Mowiol Mowiol Mowiol Mowiol Mowiol

4-98 10-98 20-98 56-98 28-99

0 0 20 40 60 80 100 Relative humidity at 23C

Figure 3 Water absorption of fully hydrolysed Mowiol grades in granular form

The Mowiol Range

very strong strong strong strong strong strong medium medium

Polyvinyl alcohol Partially hydrolysed H C O H Fully hydrolysed H C O H H C H H C O H H C H H C O H H C H H C O H H C H H C O H C H C O H C H CH3

Atom grouping C=O COC

Resonance absorption (wave number in cm1) 1 735 1 245

The Mowiol Range

Degree of hydrolysis mol% 99

500 cm1 Wave number